Scholarly article on 2,2'-[oxybis(ethane-2,1-diyloxy)]bis[2-methylpropane] 107-79-9 from Dalton Transactions p. 3880

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DOI: 10.1039/C8DT00109J

Dalton Transactions

ARTICLE

Diastereoselective synthesis, structure and reactivity studies

of ferrocenyloxazoline gold(I) and gold(II) complexes

Received 00th January 20xx,

Accepted 00th January 20xx

a

Julia Holz, Marta Ayerbe García, Wolfgang Frey, Felix Krupp and René Peters*

DOI: 10.1039/x0xx00000x

In the last decades gold complexes have demonstrated a huge potential for soft Lewis acid catalysis. Despite the intensive

research on Au complexes and planar chiral metallacycles, enantiopure ferrocenylgold complexes have – surprisingly – not

been reported until the studies presented in this article. Here we report the asymmetric synthesis of planar chiral

www.rsc.org/

2

ferrocenyl Au(I) complexes. These dinuclear species form helically chiral ten-membered (NCCCAu) rings stabilized by

aurophilic interactions. In supramolecular solid state structures linear, zigzag or helical Au(I) wires with regular Au...Au

separations were observed. The dissolved dinuclear entities could be oxidized by Au(I) to unique ferrocenyl Au(II)

complexes featuring short Au(II)–Au(II) bonds, while the ferrocene core remained intact. However, our initial studies

revealed the issue of configurational lability of the ferrocenyl Au(II) complexes in terms of the element of planar chirality in

2

the presence of the gold source, (Me S)AuCl. This was successfully addressed by a systematic study implementing

permanent -donor ortho-protecting groups like methyl or trimethylsilyl, which impede an epimerization event. Oxidation

of the dinuclear Au(I) complexes was also accomplished by oxidative addition reactions with halogenated solvents,

preferably CHCl

reactive alkylhalides like iodomethane, benzylbromide and benzyliodide. Interestingly the whole spectral range of colors

violet, blue, green, yellow, red) is covered by the title complexes depending on the Au oxidation state and the anionic

3

. Additional reactivity studies revealed that dinuclear Au(II) dihalide complexes are also formed with

(

ligands in the Au(II) complexes. This appears to be quite unusual for ferrocenes, which typically adopt orange to red colors

in a non-oxidized state.

Despite the prominent role of gold(I) in catalysis during the last

two decades and the high efficiency of the above mentioned

planar chiral ferrocenyl pallada- and platinacycles as

Introduction

Enantiomerically pure planar chiral palladacycles based on a

,2-disubstituted ferrocene core have been reported as

asymmetric catalysts, enantiomerically pure planar chira₆l

ferrocenyl gold complexes were prior to our study unknown.

Only few achiral or racemic ferrocenylgold(I) complexes were

1

versatile catalysts for asymmetric synthesis. They enabled the

development of various synthetically attractive highly

enantioselective catalytic applications. The corresponding

planar chiral platinacycles revealed a complementary potential

7

2

,3

described previously and not much is known about their

reactivity. Recently, we have reported a preliminary study

showing the first cases for the asymmetric synthesis of planar

4

for carbophilic enantioselective catalysis.

8

chiral ferrocenyl Au complexes. This study included the first

Next to the wide application of Pd(II) and Pt(II) complexes as

soft Lewis acid catalysts, in particular the use of gold(I)

complexes has been demonstrated to offer a huge synthetic

examples of dinuclear planar chiral auracycles featuring two

Au(II) centers, which form

 in good agreement with the

5

relatively small number of other bimetallic Au(II) complexes

potential. The impact of these carbophilic metals is explained

9

-11

carrying linker ligands a short Au(II)–Au(II) bond.

by the fact that they can catalyze a number of unique synthetic

transformations capable of creating a large degree of

structural complexity in an atom-economic fashion using

simple starting materials. In addition, many functional groups

are well tolerated due to the low oxophilicity of the carbophilic

metal centers. For the same reason the catalysts often do not

need rigorously inert reaction conditions and are thus easy to

In this article we provide a detailed account on the asymmetric

synthesis of planar chiral ferrocenyloxazoline gold(I) and

gold(II) complexes.

A special focus was put on the

implementation and stability effect of different relative

configurations in terms of the element of planar chirality, the

elucidation of the structural properties and a reactivity study

of the Au(I) complexes in oxidative addition reactions as a

possible entry for Au(I/II) catalyzed cross-coupling reactions.

5

handle.

a.

Universität Stuttgart, Institut für Organische Chemie, Pfaffenwaldring 55, 70569

Results and discussion

Stuttgart, Germany. E-mail: rene.peters@oc.uni-stuttgart.de

Electronic Supplementary Information (ESI) available: NMR, UV-Vis spectra and cif

files. See DOI: 10.1039/x0xx00000x

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Journal Name

Synthesis of (S )-configured ferrocenyl Au(I)- and Au(II)-complexes A ten-membered (NCCCAu)₂ring is present within each

p

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DOI: 10.1039/C8DT00109J

dinuclear entity, which contains a significant Au(I)...Au(I)

from (S)-valinol derived oxazoline iPrFO

interaction (distances: 2.8449(3) & 2.8452(3) Å). In contrast,

the Au...Au interaction between both dimers is significantly

longer (separation: 3.0651(3) Å). The tendency to undergo

Our studies started by diastereoselective ortho-lithiation of (S)-

valinol derived 2-ferrocenyloxazoline iPrFO (please see

footnote § regarding the compound code used in this article)

13,5

12

Au...Au interactions is a well-known characteristic of gold.

using previously reported conditions. Subsequent trapping of

The metal...metal distances mostly have ranges between 2.75

and 3.4 Å, and are usually formed perpendicular to the

the generated organolithium species by (Me S)AuCl provided

2

the dinuclear Au(I) complex iPrFOAu(I) in good yield (Scheme

I

5

1

principle axis of the two-coordinate Au centers. This

characteristic known as “aurophilicity” has been reported to

also allow for the formation of gold clusters and

1

). Only one diastereomer was detected by H-NMR.

Scheme 1 Asymmetric synthesis of the dinuclear ferrocenyl oxazoline Au(I)

complex iPrFOAu(I)

1

4

.

supramolecular structures. This phenomenon is explained by

dispersive (van der Waals) forces and (virtual) charge transfer,

15

leveraged by relativistic effects.

The intermolecular Au...Au interaction of the tetranuclear

entity iPrFOAu(I) also represents a chirality axis (torsion angle

Au-Au-Au-Au: –74.51(1)°). There is a strong twist within the

ten-membered rings introducing helical chirality as well.

In the supramolecular structures tetrameric entities are linked

to Au(I) helices by long, yet constant Au(I)...Au(I) separations

16

of 4.5521(3) Å between the Au termini (Figure 2).

Suitable crystals of iPrFOAu(I) for X-ray crystal structure

analysis were obtained by slowly evaporating a solution in n-

pentane at room temperature. iPrFOAu(I) adopts a C₂-

symmetric tetranuclear solid state structure (Figure 1), in

which two dinuclear gold(I) complexes bearing a bridging pair

Fig. 2 Representation of the supramolecular Au(I) helices of iPrFOAu(I)

.

of anionic C,N-ligands adopting

arrangement are linked by an intermolecular Au(I)...Au(I)

interaction.

a

head-to-tail ligand

The C-Au bonds (1.986(5)-2.000(5) Å) of iPrFOAu(I) are

somewhat shorter (ca. 2-7 pm) than for reported racemic

7

e,f

1

13

ferrocenylgold phosphine adducts. Because the H- and C-

NMR spectra of iPrFOAu(I) are relatively simple with a single

set of signals, the complexes are probably dinuclearly

organized in solution. Otherwise, the spectra would be

expected to show more signals because the ferrocenes in the

corresponding tetramers are not all equivalent. The dinuclear

nature in solution is also supported by ESI mass spectroscopy.

New species were observed by using an excess of (Me S)AuCl

2

during the carbanion trapping. A 1:1.2 mixture of two

diastereomeric

Au(II)

–Au(II)

bond-bridged

auracycles

iPrFOAu(II)Cl and epi-iPrFOAu(II)Cl was formed. iPrFOAu(II)Cl

1

should be C symmetric (as indicated by a single H-NMR signal

2

set) and epi-iPrFOAu(II)Cl C₁symmetric (Scheme 2). During

this reaction a golden mirror was formed in the reaction flask.

The formation of Au metal and Au(II) complexes through

10a,8,17

disproportionation of Au(I) is rare.

Bimetallic diamagnetic Au(II) complexes have attracted

9

-11,17-20

considerable attention during the last years,

but are

still relatively rare. The classic procedure to access this type of

compounds is via oxidation of dinuclear gold(I) complexes

carrying anionic three-atom-linker ligands using reagents such

18

as Cl , Br , I , benzoyl peroxide or CH I. However, the

2

3

formation of gold(II) complexes has also been achieved via

1

0a

oxidation by the solvent.

With chlorinated solvents long

Fig. 1 X-ray single crystal structure analysis of iPrFOAu(I). Hydrogen atoms are

omitted for clarity in all pictures of solid state structures. CCDC-number:

reaction times (2-7 days) were usually needed in order to

completely oxidize the dinuclear Au(I) compounds.

1

056862. Color code: C (black); N (blue); O (red); Fe (red); Au (golden).

2

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Three new bonds are formed during the oxidation processes, decomplexation is suggested to be facilitated by coordination

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DOI: 10.1039/C8DT00109J

between the two gold centers and the halogen atoms.

of the Cp unit to the Au source.

Scheme 2 Partial epimerization in the synthesis of dinuclear ferrocenyl oxazoline

Au(II) complexes derived from (S)-valinol.

Both diamagnetic Au(II) complexes iPrFOAu(II)Cl and epi-

iPrFOAu(II)Cl possess a deep violet color. They provided

suitable crystals for X-ray analysis (Figure 3), which were

grown by slowly evaporating a solution of iPrFOAu(II)Cl in

CH Cl and a solution of iPrFOAu(II)Cl and epi-iPrFOAu(II)Cl in

2

CH Cl /n-pentane.

2

By the X-ray analyses, the oxidation of both gold centers to

Au(II)Cl and their square planar coordination geometry with a

Au(II)–Au(II) bond (explaining the diamagnetic behaviour)

could be confirmed. The oxidation resulted in a strong

decrease of the intermetallic distance to 2.5654(3) Å for

iPrFOAu(II)Cl and 2.5333(5) Å for epi-iPrFOAu(II)Cl. The short iPrFOAu(II)Cl (bottom). CCDC-numbers: CCDC 1056863 (iPrFOAu(II)Cl) and CCDC

Fig. 3 X-ray single crystal structure analyses of iPrFOAu(II)Cl (top) and epi-

1

056865 (epi-iPrFOAu(II)Cl). Color code: C (black); N (blue); O (red); Fe (red); Au

intermetallic separations observed in these complexes are in (golden); Cl (green).

accordance with other bimetallic Au(II)-complexes reported in

1

0a

the literature. iPrFOAu(II)Cl and epi-iPrFOAu(II)Cl are to our Access to diastereomerically pure iPrFOAu(II)Cl could also be

knowledge the first reported cyclometallated Au(II)-complexes achieved by oxidation of iPrFOAu(I) with (Me S)AuCl at 0 °C

2

19

with C,N-ligands. Other bimetallic Au(II)-complexes carrying reducing the reaction time to 15 min. Significantly longer

linker ligands usually make use of atom-linkers. reaction times provided ca. 1:1 mixtures of iPrFOAu(II)Cl and

iPrFOAu(II)Cl epi-iPrFOAu(II)Cl are to our knowledge also the epi-iPrFOAu(II)Cl. Diastereomerically pure iPrFOAu(II)Cl could

first dinuclear Au(II)-complexes possessing two 4-atom C,X- also be obtained by heating a solution of iPrFOAu(I) in CH Cl₂

3

/

2

0

linkers. Both auracycles also present the element of helical under N for five days. In this case CH Cl has the role of both

2

22

chirality as already observed in complex iPrFOAu(I)

.

solvent and oxidizing agent (Scheme 3).

From these

A surprising fact revealed by the X-ray crystal structure observations it can deduced that the epimerization is likely to

analysis of compound epi-iPrFOAu(II)Cl was that the be facilitated by the gold source.

substituted Cp-ligand of one ferrocene unit was coordinating All attempts to oxidize iPrFOAu(I) by different silver salts gave

to a gold center formally through the other ortho positioned decomposition instead. In general compounds iPrFOAu(II)Cl

carbon donor atom as compared to iPrFOAu(I). This partial and epi-iPrFOAu(II)Cl proved to be quite stable towards air

epimerization phenomenon might be explained by the and moisture, as no decomposition was observed under air

electron-withdrawing character of the Au(II) centers that after several weeks at 22 °C.

might facilitate a decomplexation of the disubstituted Cp- Most of the earlier dinuclear Au(II) complexes can be isolated,

+

ligand from the CpFe moiety and its recomplexation with the however, they often exhibit a tendency to decompose into the

19

other diastereotopic face. The less electron rich the corresponding Au(I)/Au(III) compounds. Such a tendency was

substituted Cp ligand is, the easier this decomplexation should not observed for the Au(II) complexes described in this study.

be. Similar observations have already been reported before for

21

other

planar

chiral

ferrocenes.

The

reversible

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Separation of the pure (R ,R )-configured major isomer was

p

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DOI: 10.1039/C8DT00109J

Scheme 3 Epimerization-free synthesis of dinuclear ferrocenyl oxazoline Au(II)

complexes derived from (S)-valinol.

achieved by crystallization from CH Cl /n-pentane. Red needle

2

shaped crystals were obtained suitable for X-ray crystal

structure analysis (Figure 4).

Synthesis of (R )-configured ferrocenyl Au(I)- and Au(II)-complexes

p

from (S)-valinol derived oxazoline iPrFO

Because planar chirality of ferrocenes is often a very efficient

23

control element in asymmetric catalysis, we were interested

in getting access to both (S_p)- and (R )-configured

p

diastereomers possessing identical chiral information within

the ortho-directing group (e.g. an (S)-configured oxazoline

moiety). Recently, a method was developed that permits

diastereodivergency

ferrocenyloxazolines. In

in

the

ortho-metalation

presence of di-tert-

of

butyldiethylenglycol it was possible to produce the otherwise

rare planar chiral diastereomers as the major products (dr

2

4,25

values up to 7:1).

Application of this additive under slightly modified reaction

conditions also allowed for the preferred generation of (R_p)-

configured ferrocenyl gold moieties (Scheme 4). Owing to

formation of dimeric complexes, the stereochemical situation

is relatively complicated delivering a mixture of (R ,R )-,

p

(

R ,S )- and (S ,S )-isomers with a ratio of 7.0 : 1.0 : 2.7,

p p p p

respectively, in 42% yield. That means the overall ratio of (R_p)-

and (S )-configured ferrocenyl gold units is 3.55:1.

p

Scheme 4 Preparation of the epimeric dinuclear ferrocenyl oxazoline Au(I)

complexes derived from (S)-valinol.

p

Fig. 4 X-ray single crystal structure analysis of (R )-iPrFOAu(I). Top view:

molecular representation of the dimeric entity; bottom view: supramolecular

arrangement of the dimers in the crystals forming linear gold chains; CCDC-

number: CCDC 1588445. Color code: C (black); N (blue); O (red); Fe (red); Au

(

golden).

In contrast to the solid state structure of its (S ,S )-configured

p

isomer described above, (R )-iPrFOAu(I) did not form

p

tetrameric aggregates in the solid state. In this case the Au

atoms of the dimeric species form a regular linear sequence. In

this polymeric chain of Au centers a Au...Au distance of

Using the same lithiation conditions, but trapping with

iodomethane as electrophile instead, a diastereomeric ratio of

7

:1 was obtained, in agreement with Arnott’s work. This

3

.9306(5) Å was found which is considerably shorter than the

Au...Au separations between the Au termini of the tetramers

vide supra), but longer than the intermolecular Au...Au

suggests that under the reaction conditions using the gold

electrophile the (R )-configured ferrocenyl gold(I) units of (R )-

p

(

iPrFOAu(I) might either not be configurationally stable under

the reaction conditions with regard to the element of planar

chirality or the minor diastereomer of the organolithium

intermediate is maybe more reactive for the trapping reaction

separation within the tetramers.

In the dimeric entities of (R )-iPrFOAu(I) the intermetallic

p

distance amounts to 2.8518(5) Å, which is comparable to

iPrFOAu(I). In contrast to the latter the unsubstituted Cp-

ligands of both ferrocene moieties point toward each other

within the dimeric units. Also here, the 10 membered rings

with (Me S)AuCl, because conversion was not full.

2

4

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form a helical twist (N1-Au2-Au1-N2 = 141.1(3)°; C1-Au1-Au2-

C17 = 145.8(4)°; C1-Au1-Au2-N1 = 37.1(3)°; C17-Au2-Au1-N2

35.9(3)°.

Scheme 5 Diastereoselective synthesis of iPrFOMeAu(I) and iPrF

DOI: 10.1039/C8DT00109J



=



From the crystallization experiments, it was also possible to

separate darker crystals than those of (R )-iPrFOAu(I). X-ray

p

crystal structure analysis identified the corresponding (R ,R )-

p

configured Au(II)-Dimer (R )-iPrFOAu(II)Cl, which was probably

p

formed by slow oxidation with CH Cl . The Au(II)–Au(II) bond

2

length of 2.5586(6) Å is comparable to (S )-iPrFOAu(II)Cl and

p

epi-iPrFOAu(II)Cl. The helical twist of (R )-iPrFOAu(II)Cl is

p

similar to its Au(I) counterpart (N1-Au2-Au1-N2 = 125.7(3)°;

C1-Au1-Au2-C17 = 130.1(4)°; C1-Au1-Au2-N1 =

C17-Au2-Au1-N2 = 52.4(3)°).

51.8(3)° and



iPrFOMe was then deprotonated at the diastereotopic ortho-

position with t-BuLi (1.05 equiv) in Et O at 0 °C for 30 min at

2

2c

0

°C. The Au–C bonds were installed by subsequent

treatment with a substoichiometric amount of (Me S)AuCl (0.9

2

equiv) in order to avoid formation of the corresponding

gold(II) complex as side product. After filtration over celite,

washing with water and precipitation from CH Cl /n-pentane

2

iPrFOMeAu(I) was isolated in 88% yield (based on the gold

source) in almost diastereomerically pure form. Gratifyingly,

isomerization of the planar chiral ferrocene cores is avoided

with the installed methyl protecting groups.

iPrFOMeAu(I) formed single crystals from a petroleum

ether/ethylacetate (6:1) solution which were suitable for X-ray

single crystal structure analysis. The latter confirmed the

expected (R ,R )-configuration (Figure 6).

p

Similar to (R )-iPrFOAu(I) the Au atoms of the dimeric

p

Fig. 5 X-ray single crystal structure analysis of (R

CCDC 1588443. Color code: C (black); N (blue); O (red); Fe (red); Au (golden); Cl

green).

p

)-iPrFOAu(II)Cl. CCDC-number:

complexes form regular supramolecular nearly linear

sequences with slightly longer intermolecular Au...Au

separations of 3.6959(4) Å. In the dimeric entities a Au...Au

separation of 2.8549(4) Å was determined. Again, the

unsubstituted Cp-ligands of both ferrocene moieties point

toward each other within the dimeric units and the 10

membered rings show a helical twist (N1-Au1A-Au1-N1A =

(

Due to the epimerization problem and the formation of

isomeric mixtures, a different approach was developed, in

which one diastereotopic ortho-position was selectively

blocked by a permanent protecting group prior to installation

of the Au center at the other ortho-C-atom. A methyl group

was chosen as protecting group, because of (1) the relative

ease of its installation by diastereoselective ortho-lithiation

and subsequent trapping with iodomethane; (2) the relatively

small bulk of a methyl moiety to avoid significant repulsive

1



40.3(3)°; C1-Au1-Au1A-C1A = 147.7(3)°; C1-Au1-Au1A-N1 =

36.0(2)°; C1A-Au1A-Au1-N2 = 36.0(2)°. Like expected, the



geometrical influence of the methyl groups is thus minimal.

interactions not present in (R )-iPrFOAu(I) and (3) the

p

electron-donating properties of a methyl group, which might

be beneficial to avoid an epimerization of the ferrocene units

(vide supra).

The required ortho-lithiation was done in toluene for 2 h at



78 °C using n-BuLi (1.5 equiv) as base and TMEDA (2.0 equiv)

2

4a

as additive (Scheme 5).

Trapping with iodomethane

delivered a quantitative yield of an almost diastereomerically

pure methylation product performing the reaction of a 20 mg

scale. On a 700 mg scale the yield of isolated product iPrFOMe

was 90%.

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This compound proved to be remarkably stable. Attempts to

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DOI: 10.1039/C8DT00109J

remove the silyl group under basic conditions were all fruitless,

because no conversion took place even under quite harsh

reaction conditions (1M TBAF for 3 h in THF at 65 °C, or DME at

9

0 °C; or K CO , MeOH, CH Cl , 22 °C, 3 h or KOtBu, DMSO, 22

2 3 2 2

°C, overnight) and iPrFOTMSAu(I) was fully recovered. Because

desilylations of ortho-silylated ferrocenyloxazolines have been

26

previously reported, it seems that the C-Si bonds are

somehow stabilized by the gold centers.

Fig. 7 X-ray single crystal structure analysis of iPrFOTMSAu(I). CCDC-number:

CCDC 1588453. Color code: C (black); N (blue); O (red); Fe (red); Au (golden); Si

(

turquois).

Synthesis of ferrocenyl Au(I)-complexes from other chiral

enantiopure oxazolines

Next to enantiopure oxazoline iPrFO, we also employed

ferrocenyloxazolines derived from (S)-tert.-leucinol, (1R,2S)-

aminoindanol and (1S,2R)-2-amino-1,2-diphenylethanol to

synthesize the corresponding homochiral dinuclear gold

complexes (Table 1). For tBuFOMeAu(I) the solid state

structure could be determined by X-ray analysis (Figure 8). It is

very similar to the corresponding iPr-substituted oxazoline

iPrFOMeAu(I) derivative (N1-Au1A-Au1-N1A = 139.4(1)°; C1-

Fig. 6 X-ray single crystal structure analysis of iPrFOMeAu(I). Top view:

molecular representation of the dimeric entity; bottom view: supramolecular

arrangement of the dimers in the crystals forming zigzag gold chains; CCDC-

number: CCDC 1588446. Color code: C (black); N (blue); O (red); Fe (red); Au

(

golden); Cl (green).

Further advantages of the protecting group strategy next to

complete stereoselectivity and increased configurational

stability might be provided by the option that the electronic

and steric properties at the gold centers could be fine-tuned

by different ortho-substituents installed. Next to a methyl

group we also introduced the relatively bulky and electron rich

Au1-Au1A-C1A = 143.8(2)°; C1-Au1-Au1A-N1 =

Au1A-Au1-N2 = 38.4(1)°), but the intramolecular Au...Au

separation of 2.8036(2) Å is about 2% shorter.

38.4(1)°; C1A-



26

trimethylsilyl group. Its installation proceeded with good

yield and high diastereoselectivity (Scheme 5).

The subsequent installation of the gold(I) centers was again

done with a substoichiometric amount of the gold source and

provided the dinuclear complex iPrFOTMSAu(I) in good yield.

Only one diastereomer was detected thus showing that also in

this case an isomerization with regard to the element of planar

chirality could be avoided by the silyl group.

The X-ray crystal structure analysis of iPrFOTMSAu(I) is

depicted in Figure 7. The dimeric complexes form regular

almost linear supramolecular sequences with intermolecular

and intramolecular Au...Au separations of 3.7147(3) Å and

2

.8436(3) Å, respectively. Overall, the conformational effect of

the silyl group is rather small in the solid state despite its bulk Fig. 8 X-ray single crystal structure analysis of tBuFOMeAu(I). CCDC-number:

CCDC 1588450. Color code: C (black); N (blue); O (red); Fe (red); Au (golden).

(N1-Au1A-Au1-N1A = 137.9(2)°; C1-Au1-Au1A-C1A = 146.3(3)°;

C1-Au1-Au1A-N1 = 37.9(2)°; C1A-Au1A-Au1-N2 = 37.9(2)°).



6

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Table 1 Investigation of Different Oxazolines.

the homo- and the heterodimers provide only a sing Ar le icle signal

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set each in the NMR spectra.

DOI: 10.1039/C8DT00109J

Table 2 Investigation of Different Oxazoline Residues.

a

a,b

entry

w/x/

y/z

yield

RFOMe

config.; dr)

86

RFOMeAu(I)

(config.)

84

(

1

2

2.0/2.0/

1

.1/0.8

(R

p

; >50:1)

p p

(R ,R )

1.5/2.0/

.1.0.7

91

83

(S ,S

1

(S

p

; >50:1)

p

)

3

1.5/2.0/

.1/0.7

98

76

(S ,S

1

(S

; >50:1)

p

)

a

b

2

Yield of isolated product. Based on (Me S)AuCl.

entry

yield

FOMe/%

yield

a

a,b

R

2

R

2

FOMeAu(I)/%

dr)

(

Synthesis of ferrocenyl Au(I)-complexes from achiral oxazolines

1

2

74

94

69

(1.8:1)

In addition, achiral oxazolines were used to prepare racemic

reference compounds (Table 2) in order to learn more about

the influence of stereocenters at the oxazoline rings on the

structures. One of them carries the parent oxazolinyl residue

80

2.8:1)

(

entry 1), the other one carries two methyl groups in α-

a

b

Yield of isolated product. Based on (Me

2

S)AuCl.

position to the N-donors. In both cases, the ortho-methyl

protected Au(I) complexes were formed in good yields as

mixtures of two diastereomers via the above described

methylation/auration sequence. Because both (R )- and (S )-

configured ferrocenyl moieties are formed in equal quantities

from the achiral ferrocene precursors in the absence of

For Me FOMeAu(I) the solid state structure could be obtained

for the (S ,R )-configured isomer confirming its meso-

symmetry and dimeric aggregation (Figure 9). It crystallized

from CH Cl /n-pentane. This heterodimer like the structurally

2

p

2

described homodimers above also adopts a conformation with

stereoinformation, mixtures of C -symmetric enantiomeric

2

a



=

helical twist in the solid state (N1-Au2-Au1-N2

136.76(13)°; C1-Au1-Au2-C17 = 137.88(16)°; C1-Au1-Au2-N1

41.42(14)°; C17-Au2-Au1-N2 43.93(14)°). The

=

(R ,R )- and (S ,S )-configured homodimers and a meso-

p p p p



configured heterodimer can be formed, the latter one with an

inversion center (C -symmetric). Due to their symmetries, both

=

i

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intramolecular Au...Au separation was found to be Table 3 Investigation of Different Oxazoline Residues.

View Article Online

DOI: 10.1039/C8DT00109J

2

.8362(3) Å.

2

Fig. 9 X-ray single crystal structure analysis of Me FOMeAu(I). CCDC-numbers:

CCDC 1588455. Color code: C (black); N (blue); O (red); Fe (red); Au (golden).

Moreover, the corresponding complexes lacking the ortho-

protection were prepared in useful yields as nearly 1:1

a

b

entry

yield R

2

FOAu(I)/%

dr

mixtures of two dimers (Table 3). H FOAu(I) proved to be

2

almost insoluble in acetone and could thus be easily obtained

in pure form by simply washing the crude product with

acetone.

1

2

61

62

1.2:1

In this case a single crystal was obtained from a solution in

CHCl /n-pentane and an X-ray structure analysis of the C -

3

2

symmetric homodimer with (R ,R )-configuration was

p

successful. Like for the solid state structure of iPrFOAu(I), a

tetrameric aggregate was formed. However, the spatial

arrangement of the four gold atoms and thus the two dimeric

entities connected via an intermolecular Au1...Au3 interaction

a

b

1

Yield of isolated product. Determined by H-NMR.

(

separation 3.3487(5) Å) is different. For H FOAu(I) both

2

intramolecular Au...Au interactions (Au1...Au2 = 2.8618(6) Å

and Au3...Au4 = 2.8865(5) Å) lie above each other (separation

Au2…Au4 = 3.6654(5)), whereas in the case of iPrFOAu(I), the

Au atoms form a chain in the tetramer and also in the

supramolecular structure (vide supra). The axes of Au1...Au2

and Au3...Au4 are not perfectly parallel to each other with

dihedral angles of 5.407(15)° for Au2-Au1-Au3-Au4 and

1

78.5(3)° for N2-Au1-Au3-N4. In the absence of substituents at

the oxazolines’ C4-atoms, the helical twist is markedly reduced

N1-Au2-Au1-N2 = 160.5(3)°; C1-Au1-Au2-C14 = 158.5(4)°; C1-

Au1-Au2-N1 = 22.5(3)° and C14-Au2-Au1-N2 = 18.6(3)°). The

0-membered rings are considerably flatter than in the other

(



1

cases thus showing the structural impact of the oxazolinyl

moiety.

Fig. 10 X-ray single crystal structure analysis of

H

2

FOAu(I). CCDC-number: CCDC

1

1588461. Color code: C (black); N (blue); O (red); Fe (red); Au (golden).

8

| J. Name., 2012, 00, 1-3

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Accordingly, for the dimethyl substituted derivative the Au source could be avoided and iPrFOMeAu(II)Cl was

View Article Online

DOI: 10.1039/C8DT00109J

Me FOAu(I) with (S ,R )-configuration the twist is much larger obtained as a single C -symmetric isomer as judged from a

(

2

p

2

1

N2-Au1-Au2-N1 = 129.6(2)°; C1-Au1-Au2-C16 = 137.3(3)°; single signal set in H-NMR.

C16-Au2-Au1-N2 = 46.8(2)° and C1-Au1-Au2-N1 = 46.3(3)°). In addition, chlorinated solvents were investigated as

In the solid state the centrosymmetric space group P 21/n was oxidation agents. Albeit one step longer, this route offers the



found and a Au...Au distance of 2.8512(4) Å).

advantage of a better economic feasibility as less gold is

required. Oxidation of iPrFOMeAu(I) by and in CH Cl was

2

found to be very sluggish and 5 days at 50 °C were necessary

1

to achieve full conversion as determined by H-NMR-

spectroscopy. iPrFOMeAu(II)Cl was isolated in 56% yield by

precipitation with n-pentane.

Surprisingly, using 1,2-dichloroethane as oxidizing agent, there

was almost no conversion under the same conditions.

However, a higher reactivity was found with DCl-free CHCl₃.

After 24 h at 50 °C, the deeply violet iPrFOMeAu(II)Cl was

isolated in a yield of 87% (Scheme 7). Again no partial

epimerization was observed.

Scheme 7 Epimerization-free synthesis of ortho-protected dinuclear ferrocenyl

Au(II) complexes.

2

Fig. 11 X-ray single crystal structure analysis of Me FOAu(I). CCDC-numbers:

CCDC 1588454. Color code: C (black); N (blue); O (red); Fe (red); Au (golden).

Synthesis of enantiopure ortho-protected ferrocenyl Au(II)-

complexes

Preparation of the ortho-protected ferrocenyl-Au(II)

complexes was attempted by either using an excess of Au(I)

during carbanion trapping or by organic halides.

iPrFOMeAu(II)Cl was thus prepared in high yield from planar

chiral ligand iPrFOMe by deprotonation with tBuLi in Et O at 0

2

°

C for 30 min and subsequent treatment with 3.0 equiv of iPrFOMeAu(II)Cl crystallized from CHCl

Me S)AuCl at room temperature overnight (Scheme 6).

structure containing a relatively short Au(II)

.5126(3) Å was confirmed by X-ray single crystal structure

3

/n-pentane and its

(

–Au(II)-bond of

2

Scheme 6 Epimerization-free synthesis of ortho-protected dinuclear ferrocenyl analysis (dihedral angles: N2-Au1-Au2-N1 = 124.40(14)°; C1-

Au(II) complex iPrFOMeAu(II)Cl using an excess of (Me S)AuCl.

2

Au1-Au2-C18 = 128.92(19)°; N2-Au1-Au2-C18 =

and C1-Au1-Au2-N1 = 53.45(16)).

53.23(17)°



Similarly, the oxidation of iPrFOTMSAu(I) was performed in

CHCl at 50 °C (Scheme 7). In that case 6 days at 50 °C were

3

needed until full conversion was achieved. iPrFOTMSAu(II)Cl

was isolated in a yield of 77%.

Next to the gold(II) complexes with different ortho-protecting

groups, few gold(II) complexes differing in their oxazoline

substituents were prepared. tBuFOMeAu(II)Cl was obtained

from tBuFOMeAu(I) in 87% yield by stirring in CHCl at 50 °C

3

(Scheme 7).

Gratifyingly, and in contrast to the Au(II) complexes

iPrFOAu(II)Cl and (R )-iPrFOAu(II)Cl described above, by the

p

ortho-protection strategy an epimerization in the presence of

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Journal Name

iPrFOMeAu(II)Cl and tBuFOMeAu(II)Cl in terms of the gold

View Article Online

DOI: 10.1039/C8DT00109J

coordination spheres (Au(II)-Au(II)-bond length: 2.517(2) Å;

N1A-Au2A-Au1A-N2A =

126.7(12)°; C1A-Au1A-Au2A-C22A

=



133.5(13)°; N2A-Au1A-Au2A-C22A = 51.9(13)° and C1A-

Au1A-Au2A-N1A = 47.9(12)°). Opposite signs of the dihedral

angles illustrating the helical twist of the dimers is the

consequence of the configuration of the oxazoline moieties.

Scheme 8 Synthesis of ortho-protected Au(II) complexes bearing C(4),C(5)-

disubstituted oxazoline donors.

Fig. 12 X-ray single crystal structure analysis of iPrFOMeAu(II)Cl. CCDC-number:

CCDC 1588449. Color code: C (black); N (blue); O (red); Fe (red); Au (golden); Cl

(

green).

Its X-ray crystal structure analysis closely resembles that of

iPrFOMeAu(II)Cl (Au(II)-Au(II)-bond length: 2.5269(2) Å; N2-

Au1-Au2-N1 = 126.75(13)°; C1-Au1-Au2-C18 = 130.09(17)°; N2-

Au1-Au2-C18

52.33(15)°).

=



50.83(16)°

and

C1-Au1-Au2-N1

=



Fig. 13 X-ray single crystal structure analysis of tBuFOMeAu(II)Cl. CCDC-number:

CCDC 1588447. Color code: C (black); N (blue); O (red); Fe (red); Au (golden); Cl

green).

(

Fig. 14 X-ray single crystal structure analysis of IndFOMeAu(II)Cl. CCDC-

numbers: CCDC 1588452. Color code: C (black); N (blue); O (red); Fe (red); Au

(

golden); Cl (green).

In the same way IndFOMeAu(I) was oxidized by CHCl at 50 °C

3

to give IndFOMeAu(II)Cl in 75% yield (Scheme 8). The reaction In the same way Ph FOMeAu(II)Cl was prepared in 69% yield

2

was slower than for the other ortho-Me protected Au(I) (reaction time: 6 d). Its Au(II)

–Au(II)-bond length of 2.5106(6) Å

precursors, which might be a result of the steric bulk of the was the shortest found in the investigated series (Figure 15).

tricyclic oxazolines, and thus required 4 days for complete Nevertheless, the structure is quite similar to the other Au(II)

conversion.

The structural parameters determined by X-ray crystal Au2A-C28A =

structure analysis are also in this case quite similar to C1A-Au1A-Au2A-N1A = 52.3(5)°).

Cl complexes (N1A-Au2A-Au1A-N2A =

127.6(4)°; C1A-Au1A-



127.4(5)°; N2A-Au1A-Au2A-C28A = 52.7(5)° and

1

0 | J. Name., 2012, 00, 1-3

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View Article Online

DOI: 10.1039/C8DT00109J

Fig. 15 X-ray single crystal structure analysis of Ph

2

FOMeAu(II)Cl. CCDC-

numbers: CCDC 1588451. Color code: C (black); N (blue); O (red); Fe (red); Au

(

golden); Cl (green).

Reactivity studies

A single crystal of iPrFOMeAu(II)Br was used for X-ray

Because the bimetallic oxidative additions proceeded even structure analysis (Figure 16). By the bromine atoms the

with the relatively inert chlorinated solvents, reactivity studies Au(II) Au(II)-bond length 2.5262(3) Å was slighter longer than

–

were performed treating iPrFOMeAu(I) with various for the corresponding chloro derivative (2.5126(3) Å). The

electrophilic organic halides, which might be interesting for helical twist is very similar for both compounds (dihedral

possible Au(I)/Au(II) catalyzed C-C-coupling reactions with angles for iPrFOMeAu(II)Br: N2-Au1-Au2-N1 = 124.10(16)°; C1-

nucleophilic coupling partners. The large majority of reported Au1-Au2-C18 = 128.1(2)°; N2-Au1-Au2-C18 =

gold catalyzed reactions is based on -activation modes of C1-Au1-Au2-N1 = 53.40(18)°).

54.41(19)° and





5

unsaturated substrates. The cause to the initial disinterest in

the redox gold catalysis could be explained by the high redox

I

III

potential between Au and Au . Oxidative additions with Au(I)

27

are usually kinetically challenging, but during the past few

2

8

years some breakthrough examples have been reported.

Treating iPrFOMeAu(I) with an excess of benzylbromide in

toluene at 50 °C for 24 h, not the expected C -symmetric Br

–

1

Au–Au–Bn containing complex iPrFOMeAu(II)Br/Bn was

obtained, but the corresponding ink-blue colored dibromide

iPrFOMeAu(II)Br (Scheme 9, 50% yield). As a side reaction,

ligand-ligand coupling was observed providing the

29

corresponding bisferrocene (iPrFOMe)₂

.

Using the less reactive electrophile ethylbromide and a

pressure tube under otherwise identical reaction conditions,

no reactivity was detected. Surprisingly, the same was found

for the brominating agent 1,2-dibromoethane. In contrast, 1,2-

dibromotetrachloroethane (6 equiv) in CH Cl at room

2

temperature furnished iPrFOMeAu(II)Br. After 30 min and

washing with n-pentane to remove all reagent it was obtained

in excellent yield (98%). In this case, directly after addition of Fig. 16 X-ray single crystal structure analysis of iPrFOMeAu(II)Br. CCDC-number:

CCDC 1588448. Color code: C (black); N (blue); O (red); Fe (red); Au (golden); Br

the brominating agent, the characteristic blue color of (red).

iPrFOMeAu(II)Br was visible.

iPrFOMeAu(I) was also treated with freshly prepared

benzyliodide in toluene at room temperature for 2 h

3

0

Scheme 9 Synthesis of ortho-protected dinuclear ferrocenyl Au(II) complex (Scheme 10). After 2 h the solvent was removed and the crude

2 2

iPrFOMeAu(II)Br by oxidation with BnBr and (BrCl C) . The dashed box shows the

ferrocene coupling side-product for the upper reaction.

product washed with n-pentane, furnishing a green, light-

sensitive complex with a similar H-NMR spectrum as

1

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iPrFOMeAu(II)Cl and iPrFOMeAu(II)Br, but with a downfield- After stirring overnight at room temperature in CH Cl in the

View Article Online

2 2

DOI: 10.1039/C8DT00109J

filtration to remove AgCl

shifted single signal set. ESI-MS confirmed that this solid is absence of light and

a

iPrFOMeAu(II)I. Due to its sensitivity in solution and towards iPrFOMeAu(II)OAc could be isolated in almost quantitative

light, perfectly pure samples of iPrFOMeAu(II)I could not be yield by washing with n-pentane (Scheme 11).

obtained.

Scheme 11 Synthesis of iPrFOMeAu(II)OAc by anion exchange.

Scheme 10 Synthesis of ortho-protected iPrFOMeAu(II)I by oxidation with MeI,

BnI and I .

2

Figure 17 compares the characteristic area around 5 ppm of

1

the H-NMR spectra of the three bimetallic Au(II) complexes

iPrFOMeAu(II)Cl

, iPrFOMeAu(II)Br and iPrFOMeAu(II)I in

CD Cl . The doublets belong the Cp-protons in ortho-position

2

to the Au-C bonds. The multiplets are assigned to the

oxazoline protons at the stereocenters. As a general trend

there is a low-field shift with increasing atomic number of the

halide ligands for the signals of these H atoms in spatial

proximity to the Au(II) centers pointing to electronic

differences caused by the halide ligands. This might be

explained by weaker connections of bromide and iodide to

the harder ferrocenyl gold(II) centres (compared to gold(I)),

whereas chloride might contact more strongly. Weaker

interactions would increase the cationic character of the

gold(II) centres and might cause a downfield shift.

In early studies Schmidbaur and Franke reported the oxidative

addition of iodomethane and iodine to dimeric phosphonium-

methylid Au(I) complexes. Similarly, we also investigated the

use of iodomethane (Scheme 10). Treatment of a solution of

iPrFOMeAu(I) in toluene with an excess of MeI (1.5 equiv) at

9a

5

0 °C for 3 h again provided iPrFOMeAu(II)I (46% after flash

31

column chromatography). Like with BnBr, bisferrocene

iPrFOMe)₂was found as a side product, isolated in 9% yield.

In addition, we found the dimethylated ligand (iPrFOMe₂

3%), in which Au was replaced by another methyl substituent.

This might have occurred via the expected initial product of a

bimetallic oxidative addition containing the Me Au(II) Au(II)I

fragment and reductive elimination. Another ferrocenyl

containing complex was also present, but its structure could

not be unambiguously assigned. It might have been the

(

1

Fig. 17 Detail of the H-NMR spectra at ca. 5 ppm of iPrFOMeAu(II)Cl (red),

,

iPrFOMeAu(II)Br (blue) and iPrFOMeAu(II)I (green).

2

Electronic differences of the Au(II) complexes are also

refelcted by the different colors, both in solution and solid

state. Figure 18 shows solutions of iPrFOMeAu(II)Cl (purple),



iPrFOMeAu(II)Br

(blue),

iPrFOMeAu(II)I

(green),

iPrFOMeAu(II)OAc (red), and iPrFOMeAu(I) (yellow-orange),

covering the whole visible spectral range, which appears to be

quite unusual for ferrocenes.

Me



Au(II)



Au(II)

I containing complex, because the fragment



[

M-I] = 1029.14 m/z with the expected isotopic pattern was

detected by ESI-MS. However, its isolation was unfortunately

not successful.

In addition, iPrFOMeAu(II)I was obtained in 40% yield by

oxidation of iPrFOMeAu(I) with I (1.0 equiv) in CH Cl at room

2

temperature. Due to the sensitivity of iPrFOMeAu(II)I, rapid

chromatography and removal of solvent was always required

1

plus storage in the dark in order to obtain satisfying H-NMR

13

spectra. On the other hand, recording satisfying C-NMR

spectra was impeded by the required prolonged acquisition

times.

The dimeric gold(II) complex iPrFOMeAu(II)Cl was also used

for an anion exchange reaction with silver acetate (2.0 equiv).

Fig. 18

iPrFOMeAu(II)I (green), iPrFOMeAu(I) (yellow-orange) and iPrFOMeAu(II)OAc

red).

Solutions of iPrFOMeAu(II)Cl (purple), iPrFOMeAu(II)Br (blue),

(

1

2 | J. Name., 2012, 00, 1-3

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Figure 19 shows the corresponding UV-Vis spectra. The lowest

energy maxima in these curves are probably caused by MLCT

Experimental

General Considerations. All reactions were performed in dried

glassware (24 h at 150 C in an oven or 5 min at 650 C in

vacuo) under a positive pressure of nitrogen (ca. 1.2 bar).

Liquids were added via syringe. Solvents were evaporated at

40 °C and 600−10 mbar. Yields are given, if not indicated

View Article Online

DOI: 10.1039/C8DT00109J

(Fe→oxazoline) for the Au(I) and MMCT (Fe→Au) for the Au(II)

°

complexes. There is a lower-energy-shift for the absorption of

all four Au(II) complexes compared to the Au(I) complex

(

maximum at 461 nm) which might be explained by the

8

electron-withdrawing properties of the Au(II) centers. The

otherwise, with regard to the isolated, analytically pure

product. CH Cl , diethyl ether, tetrahydrofurane and toluene

strongest shift is found for iPrFOMeAu(II)I (maximum at

2

6

06 nm) in this series, followed by the corresponding bromide

were dried by a solvent purification system. DMF und 1,2-DCE

were purchased in crown-capped bottles and used without

further purification. Technical grade solvents used for workup

and purification such as CH Cl , ethyl acetate, petroleum

(575 nm), chloride (543 nm) and acetate (487 nm) complexes.

Full theoretical analysis, electronic and electrochemical

properties of the title compounds will be discussed later.

2

ether, and acetone were distilled prior to use, whereas CHCl₃

was filtered over aluminum oxide 90 active basic (0.06-

0

.20 mm). Ethanol and n-pentane were used without further

purification. Additional chemicals were purchased and, unless

indicated otherwise, used without further purification.

Technical TMEDA (tetramethylethylenediamine) was refluxed

with KOH and freshly distilled under nitrogen. For column

chromatography silica gel (silica 60, 0.04-0.063 mm) was used.

For thin layer chromatography (TLC), silica-gel plates (silica gel

6

0 F254) were used. Visualization occurred by fluorescence

quenching under UV light ( 254 nm) and/or by staining with

KMnO /NaOH. Deuterated solvents for NMR experiments

were stored at 4 C over molecular sieves. NMR spectra were

measured with 300/400/500/700 MHz spectrometers at 21 C.

Chemical shifts are given in ppm relative to the residual

λ

4

°

Fig. 19 UV-Vis spectra of iPrFOMeAu(I) (yellow curve), iPrFOMeAu(II)Cl (purple),

iPrFOMeAu(II)Br (blue), iPrFOMeAu(II)I (green), and iPrFOMeAu(II)OAc (red).

δ

solvent peak of the used deuterated solvent. Coupling

constants J are given in Hz with regard to multiplicity (s

(

singlet), d (doublet), t (triplet), q (quartet), m (multiplet), b

Conclusions

(broad signal)). IR spectra were measured by the analytical

In conclusion, we have reported the first asymmetric syntheses

of planar chiral ferrocenyl gold complexes. Various dinuclear

Au(I) complexes featuring two bridging monoanionic C,N-

ligands were prepared by diastereoselective ortho-lithiations

service at the Universität Stuttgart. Samples were either

measured in the solid state or, if liquid, as a solution. IR bands

-1

are given in units of wavenumbers (cm ). Optical rotation was

measured on a polarimeter operating at the sodium D line (

589 nm) and mercury lines ( 578 nm and 546 nm) with a

λ

and subsequent trapping reactions with (Me S)AuCl. In this

2

λ

1

λ2

^w^a^y^t^eⁿ^-^m^e^m^b^e^r^e^d^h^e^lⁱ^c^a^l^l^y^c^hⁱ^r^a^l⁽^N^C^C^C^A^u⁾2 rings were

formed, stabilized by aurophilic Au(I)...Au(I) interactions. These

complexes are smoothly oxidized by the Au(I) source to form

100 mm path cell length. Melting points were measured in

open glass capillaries and are uncorrected. Mass spectra (EI or

ESI) were obtained from the MS service of the Universität

Stuttgart. Single-crystal X-ray analysis was performed by Dr.

dinuclear Au(II) complexes, which feature short Au(II)–Au(II)

bonds. Helical chirality and head-to-tail ligand arrangements of

the Au(I) complexes were conserved in the Au(II) species.

However, initially we noticed partial epimerization of the

ferrocene fragments in terms of the element of planar

Wolfgang Frey (Universität Stuttgart) (Cu K

α

1.54178 Å and Mo

vis

K

α

0.71073 Å)). UV vis spectra were recorded using a UV−

−

spectrometer with deuterium and tungsten lamps operating

between 190 and 1100 nm. CD spectra were measured by

M.Sc. Heiko Bamberger (research group of Prof. J. van

chirality, probably caused by an excess of (Me S)AuCl. This

2

issue was successfully addressed by installing permanent

ortho-protecting groups on the substituted ferrocenyl Cp rings

like methyl or trimethylsilyl. Oxidation of the dinuclear Au(I)

complexes was also caused by halogenated solvents,

Slageren, Universität Stuttgart) at

spectrometer of AVIV bimedical, inc. with a HLX 64663 (400 W,

6V) lamp of Osram.

Formation of the ligands and complexes was determined by H

a model 42 MCD

3

1

13

preferably CHCl . Reactivity studies showed that dinuclear

3

and C NMR spectroscopy as well as mass spectrometry. Proof

of identity was also given by single-crystal X-ray diffraction

analyses and/or high resolution mass spectrometry. The purity

of the products was established by NMR spectroscopy. The

complexes H FOAu(I) and H FOMeAu(I) bearing the parent 2-

Au(II) dihalide complexes are also formed with reactive

alkylhalides. Intriguingly, the whole spectral range of colors

(violet, blue, green, yellow, red) can be accomplished with

these complexes depending on the Au oxidation state and the

anionic ligands in the Au(II) complexes.

2

oxazolinyl residue are quite unstable. Due to fast

decomposition in solution the samples used for NMR spectra

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Page 14 of 25

ARTICLE

Journal Name

were not perfectly pure. Elemental analyses were not complexes, it was diluted with toluene (5 mL/mm _V _i _e o _w l)_A _r _t a _i _c n _l _e d _O _n t _l h _i _n e _e

sufficient as well for these two complexes, because of reaction mixture was stirred overnight a^Dt^Or^I^:o¹o⁰m^.¹⁰³t⁹e^/m^C⁸p^De^Tr⁰a⁰tu¹⁰r⁹e^J.

insufficient thermal stability (few days at room temperature). The reaction mixture was filtered over celite with CH Cl ,

2

A proof of purity was thus not possible for these two cases. washed with water, the organic phase was dried over MgSO₄

Furthermore the iodo-complex iPrFOMeAu(II)I is quite light and the solvent was removed under reduced pressure. The

sensitive and quite unstable in solution. Because of that small crude product was purified by washing with pentane. Yields

1

3

decomposition signals can be seen in the C NMR. However, were calculated based on the amount of chloro(dimethyl

the purity of iPrFOMeAu(II)I is still relatively high. sulfide)gold(I).

General procedure for the synthesis of oxazolinylferrocene General procedure

ligands (GP1). To ferrocenecarboxylic acid, suspended in dry dichlorobisoxazolinylferrocene digold(II) complexes (GP5).

CH Cl (7 mL/mmol) and DMF (0.1 equiv) at room The corresponding gold(I) complex (1.0 equiv) was dissolved in

for

the

synthesis

of

2

4a

8

2

temperature, was added oxalyl chloride (1.5 equiv). When the CHCl (100 mL/mmol) and stirred at 50 °C. After cooling to

3

solid had completely dissolved, the reaction mixture was room temperature the reaction mixture was filtered over

stirred for further 30 min and then all volatiles were removed celite with CH Cl . The crude product was purified by washing

2

under reduced pressure. The dark red solid was dissolved in with pentane.

CH Cl (5 mL/mmol) and Et N (3.0 equiv), the corresponding Synthesis of di-tosyldiethyleneglycol.

2

4a

Diethyleneglycol

aminoalcohol (1.3 equiv) was added at 0 °C and it was stirred (3.4 g, 32.039 mmol, 1.0 equiv) was dissolved in CH Cl (52 mL)

2

3

2

for 4 h. After the addition of further Et N (3.0 equiv) and mesyl at 0 °C and treated with Et N (13.3 mL, 9.7 g, 96.118 mmol,

3

chloride (2.0 equiv) the reaction mixture was stirred at room 3.0 equiv), DMAP (391.4 mg, 3.204 mmol, 0.1 equiv) and tosyl

temperature overnight. Saturated aqueous NaHCO solution chloride (13.4 g, 70.486 mmol, 2.2 equiv). The reaction mixture

3

and CH Cl were added and the aqueous layer was extracted was stirred at room temperature overnight. Then additional

2

twice with CH Cl . The organic layers were dried over MgSO

CH Cl (30 mL) was added and the mixture was washed water

2 2

2

4

and the solvent was removed under reduced pressure. The and 1M HCl solution. The organic layer was dried over MgSO₄

crude product was purified by column chromatography over and the solvent was removed under reduced pressure. The

silica gel with PE/EE.

General procedure

crude product was crystallized in the cold over 2 days and the

for

the

synthesis

of crystals were washed with cold Et O to provide the product as

2

4a

oxazolinylmethylferrocene ligands (GP2). A solution of the white solid (12.1 g, 29.289 mmol, 91%). C H O S : MW:

corresponding oxazolinyl-ferrocene in toluene (10 mL/mmol) 414.49 g/mol. H-NMR (400 MHz, CDCl , 25 °C): δ = 7.83-7.74

1

8 22 7 2

1

3

and TMEDA (2.0 equiv) was cooled to

78 °C. n-BuLi (1.6M in (m, 4H, Ar-H), 7.39-7.31 (m, 4H, Ar-H), 4.15-4.04 (m, 4H,

hexane, 1.5 equiv) was added dropwise and the mixture was TsOCH CH O), 3.66-3.56 (m, 4H, TsOCH CH O), 2.45 (s, 6H,

2

24a

stirred for 2 h. After warming to room temperature methyl CH ). The analytical data is in accordance to literature.

iodide or trimethylsilyl chloride (2.0 equiv) was added, Synthesis of di-tert-butyldiethyleneglycol. Lithium tert-

3

2

followed by further stirring for 1 h. Et O and saturated butoxide (3.9 g, 48.252 mmol, 5.0 equiv) in tert-butyl alcohol

2

aqueous NaHCO solution were added. The organic layer was (106 mL) was treated with a solution of ditosyldiethyleneglycol

3

dried over MgSO and the solvent was removed under reduced (4.0 g, 9.650 mmol, 1.0 equiv) in THF (48 mL). The reaction

4

pressure. The crude product was purified by column mixture was stirred at reflux for 24 h. After cooling to room

chromatography over silica gel with PE/EE.

General procedure for the

oxazolinyldimethylferrocene ligands (GP3). To a solution of and the solvent was removed under reduced pressure. The

temperature petroleum ether and saturated aqueous NaHCO₃

of solution were added. The organic layer was dried over MgSO₄

synthesis

2c

the corresponding oxazolinyl-methyl-ferrocene in Et O (10- crude product was purified via distillation (bulb-to-bulb) to

2

1

5 mL/mmol), t-BuLi (1.7M in pentane, 1.1 equiv) was added provide the di-tert-butyl diethylene glycol (1.2 g, 5.515 mmol,

1

dropwise at 0 °C. Once it was stirred for 15-30 min methyl 57%) as colorless liquid. C H O MW: 218.34 g/mol. H-NMR

12 26 3:

iodide (2.0 equiv) was added and the reaction mixture was (400 MHz, CDCl , 25 °C): δ =3.66-3.56 (m, 4H, tBuOCH CH O),

3

2

stirred for further 1 h at room temperature. After the addition 3.56-3.47 (m, 4H, tBuOCH CH O), 1.19 (s, 18H, CH ). The

2

3

24a

of saturated aqueous NaHCO solution and Et O the organic analytical data is in accordance to literature.

3

2

33

layer was dried over MgSO and the solvent was removed Synthesis of (dimethylsulfide)gold(I) chloride. Chloroauric

4

under reduced pressure. The crude product was purified by acid trihydrate (1.0 g, 2.539 mmol, 1.0 equiv) was dissolved in

column chromatography over silica gel with PE/EE.

General procedure for the synthesis

bisoxazolinylferrocene-digold(I) complexes (GP4).

degassed EtOH (24.0 mL) and treated with a solution of

of dimethylsulfide (0.5 g, 556.9 µL, 7.617 mmol, 3.0 equiv) in

2

c

In

a

degassed EtOH (20.0 mL). After stirring at room temperature

Schlenk flask t-BuLi (1.7M in pentane, 1.1 equiv) was added for 2 h the reaction mixture was cooled to 0 °C, the

dropwise to a solution of the corresponding oxazolinyl-methyl- precipitation was filtered off and washed with cold EtOH (1 x

ferrocene in Et O (10 mL/mmol) at 0 °C. Once it was stirred for 1 mL) and cold Et O (2 x 1 mL). The product was dried in vacuo

2

1

5-30 min chloro(dimethyl sulfide)gold(I) (0.7-0.9 equiv) was to yield a white solid (0.7 g, 2.516 mmol, 99%). C H AuClS:

2 6

1

added. With this slight substoichiometric use of MW: 294.55 g/mol. H-NMR (400 MHz, CDCl , 25 °C): δ = 2.75

3

chloro(dimethyl sulfide)gold(I) a direct oxidation to the gold(II) (s, 6H, S(CH ) ). The analytical data is in accordance to

3

2

34

complexes was prevented. For a better solubility of the gold(I) literature.

1

4 | J. Name., 2012, 00, 1-3

This journal is © The Royal Society of Chemistry 20xx

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Page 15 of 25

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Journal Name

Synthesis

ARTICLE

of

(S)-(4-isopropyl-4,5-dihydro-2-oxazolyl) Synthesis of (4R,5S)-(4,5-5H-indeno[1,2-d]-4,5-dihydro-2-

View Article Online

DOI: 10.1039/C8DT00109J

ferrocene (iPrFO). In accordance with GP1 ferrocenecarboxylic oxazolyl) ferrocene (IndFO). According to a modified literature

acid (1.0 g, 4.347 mmol, 1.0 equiv) in CH Cl (73.0 mL) was procedure, to ferrocene carbamide (333.5 mg, 1.456 mmol,

3

6

2

treated with DMF (33.4 µL, 31.8 mg, 0.435 mmol, 0.1 equiv) 1.00 equiv) was added

and oxalyl chloride (559.2 µL, 827.7 mg, 6.521 mmol, tetrafluoroborate (287.7 mg, 1.514 mmol, 1.04 equiv) in DCE

.5 equiv). The remaining synthesis differs from GP1. After the (8.7 mL) at room temperature. The triethyloxonium

removal of all volatiles, the residue was dissolved in CH Cl tetrafluoroborate was freshly washed with dry Et O before.

a solution of triethyloxonium

1

2

(

58.0 mL), Et N (1.2 mL, 879.8 mg, 8.694 mmol, 2.0 equiv) and After 4 h the (1R,2S)-cis-1-amino-2-indanol (234.6 mg,

3

(L)-valinol (448.4 mg, 4.347 mmol, 1.0 equiv) was added. Then 1.572 mmol, 1.10 equiv) dissolved in DCE (14.6 mL) was slowly

Et N (1.8 mL, 1.3 g, 13.041 mmol, 3.0 equiv), DMAP (53.1 mg, added at 0 °C. The reaction mixture was heated to 60 °C

3

0

5

.435 mmol, 0.1 equiv) and tosyl chloride (1035.9 mg, overnight. After cooling to room temperature the mixture was

.434 mmol, 1.3 equiv) were added. Column chromatography washed with saturated aqueous NaHCO₃solution and the

(

silica gel, PE/EE = 4:1) afforded the product as orange aqueous layer was extracted with CH Cl . The organic layer

2 2

crystalline solid (961.0 mg, 3.234 mmol, 74%). C H FeNO: was dried over MgSO and the solvent was removed under

1

6

19

4

1

MW: 297.18 g/mol. H-NMR (300 MHz, CDCl , 25 °C): δ = 4.80- reduced pressure. Column chromatography (silica gel, PE/EE =

3

4

5

.70 (m, 2H, Cp-H), 4.36-4.25 (m, 3H, Cp-H, OCH CHN), 4.12 (s, 2:1 to 1:1) afforded the product as orange solid (431.2 mg,

2

H, Cp-H), 4.11-3.94 (m, 2H, OCH CHN), 1.94-1.78 (m, 1H, 1.256 mmol, 86%). C H FeNO: MW: 343.21 g/mol. MP:

2

20 17

20

1

CH(CH ) ), 1.01 (d, J = 6.8, 3H, CH(CH ) ), 0.94 (d, J = 6.8, 3H, 142 °C. [α]_D: 224.4 (c = 1.13 mg/mL, CH Cl ). H-NMR (700

CH(CH ) . The analytical data is in accordance to literature.

3

2

3 2

2

1

2a,26

MHz, CDCl , 25 °C): δ = 7.56-7.55 (m, 1H, Ar-H), 7.28-7.24 (m,

3

2

Synthesis

ferrocene

of

(S)-(4-tert-butyl-4,5-dihydro-2-oxazolyl) 3H, Ar-H), 5.59 (d, J = 7.3, 1H, NCH), 5.37-5.35 (m, 1H, OCH),

In accordance with GP1 4.75-4.71 (m, 2H, Cp-H), 4.30-4.28 (m, 2H, Cp-H), 3.99 (s, 5H,

(tBuFO).

ferrocenecarboxylic acid (1.0 g, 4.347 mmol, 1.0 equiv) in Cp-H), 3.47 (dd, J = 6.7, 17.8, 1H, CH ), 3.34 (d, J = 17.8, 1H,

2

13

CH Cl (73.0 mL) was treated with DMF (33.4 µL, 31.8 mg, CH₂). C-NMR (175 MHz, CDCl , 25 °C): δ = 166.7 (1C, C=N),

2

3

0

8

.435 mmol, 0.1 equiv) and oxalyl chloride (559.2 µL, 142.5 (1C, Ar-C), 139.6 (1C, Ar-C), 128.5 (1C, Ar-C), 127.6 (1C,

27.7 mg, 6.521 mmol, 1.5 equiv). After the removal of all Ar-C), 125.7 (1C, Ar-C), 125.4 (1C, Ar-C), 82.8 (1C, OCH), 76.9

volatiles, the residue was dissolved in CH Cl (58.0 mL), Et N (1C, NCH), 70.5 (1C, Cp-C), 70.4 (1C, Cp-C), 70.0 (1C, Cp-C), 69.7

2

3

(

1.2 mL, 879.8 mg, 8.694 mmol, 2.0 equiv) and (L)-leucinol (5C, Cp-C), 69.3 (1C, Cp-C), 69.2 (1C, Cp-C), 39.9 (1C, CH ). IR (in

2

509.4 mg, 4.347 mmol, 1.0 equiv) was added. Then Et N CH Cl ): 휈̃ = 3095, 2954, 2922, 1647, 1477, 1427, 1378, 1312,

3

2

1.8 mL, 1.3 g, 13.041 mmol, 3.0 equiv) and mesyl chloride 1290, 1238, 1110, 1021, 995, 930, 855, 823, 748, 728, 503,

420.6 µL, 622.4 mg, 5.434 mmol, 1.3 equiv) were added. 486, 445. HRMS (ESI) m/z: calculated for

H] ): 344.0732; found: 344. 0724.

afforded the product as orange solid (1142.0 mg, 3.672 mmol, Synthesis of (4R,5R)-(4,5-diphenyl-4,5-dihydro-2-oxazolyl)

5%). C H FeNO: MW: 311.20 g/mol. 1H-NMR (400 MHz, ferrocene (Ph FO). In accordance with GP1



Column chromatography (silica gel, PE/EE = 4:1 to 2:1) ([M



8

1

7

21

2

CDCl , 25 °C): δ = 4.79-4.76 (m, 1H, Cp-H), 4.71-4.69 (m, 1H, ferrocenecarboxylic acid (1.0 g, 4.347 mmol, 1.0 equiv) in

3

Cp-H), 4.34-4.30 (m, 2H, Cp-H), 4.27-4.13 (m, 2H, OCH CHN), CH Cl (73.0 mL) was treated with DMF (33.4 µL, 31.8 mg,

2

4

.19 (s, 5H, Cp-H), 3.93-3.86 (m, 1H, OCH CHN), 0.96 (s, 9H, 0.435 mmol, 0.1 equiv) and oxalyl chloride (559.2 µL,

2

12a,35

tBu). The analytical data is in accordance to literature.

Synthesis of ferrocene carbamide. At room temperature volatiles, the residue was dissolved in CH Cl (58.0 mL), Et N

827.7 mg, 6.521 mmol, 1.5 equiv). After the removal of all

36

2

3

ferrocenecarboxylic acid (2.0 g, 8.694 mmol, 1.00 equiv) was (1.2 mL, 879.8 mg, 8.694 mmol, 2.0 equiv) and (1S,2R)-2-

suspended in dry CH Cl (40 mL) and DMF (20.1 µL, 19.1 mg, amino-1,2-diphenylethanol (927.1 mg, 4.347 mmol, 1.0 equiv)

2

0

1

.261 mmol, 0.03 equiv) and oxalyl chloride (1.1 mL, 1.7 mg, was added. Then Et N (1.8 mL, 1.3 g, 13.041 mmol, 3.0 equiv)

3.0 mmol, 1.5 equiv) was added. When the solid had and mesyl chloride (420.6 µL, 622.4 mg, 5.434 mmol,

3

completely dissolved, the reaction mixture was stirred for 1.3 equiv) were added. Column chromatography (silica gel,

further 30 min and then all volatiles were removed under PE/EE = 4:1 to 2:1) afforded the product as red solid

reduced pressure. The dark red solid was dissolved in CH Cl₂(1516.8 mg, 3.724 mmol, 86%). C H FeNO: MW: 407.29

2

25 21

1

(

40 mL) and a solution of 7N ammonia in methanol (16.4 mL, g/mol. H-NMR (500 MHz, CDCl , 25 °C): δ = 7.45-7.35 (m, 7H,

3

1

.9 g, 113.0 mmol, 13.0 equiv,) was added at 0 °C over 5 min. Ph-H), 7.34-7.28 (m, 3H, Ph-H), 5.33 (d, J = 7.6, 1H, OCHCHN),

After stirring at room temperature for 4 h, demin. water was 5.09 (d, J = 7.6, 1H, OCHCHN), 4.95-4.90 (m, 2H, Cp-H), 4.45-

added and the mixture was extracted with Et O twice. The 4.41 (m, 2H, Cp-H), 4.30 (s, 5H, Cp-H). The analytical data is in

2

24a

organic layers were dried over MgSO and the solvent was accordance to literature.

4

removed under reduced pressure. The crude product was used Synthesis of 2-oxazolinyl ferrocene (H FO). In accordance with

2

for the next step without purification. C H FeNO: MW: GP1 ferrocenecarboxylic acid (510.0 mg, 2.217 mmol,

1

1 11

1

2

29.06 g/mol. H-NMR (400 MHz, CDCl , 25 °C): δ = 5.49 (br, 1.0 equiv) in CH Cl (15.0 mL) was treated with DMF (17.1 µL,

3 2 2

2

H, NH ), 4,68 (t, J = 2.0, 2H, Cp-H), 4.39 (t, J = 2.0, 2H, Cp-H), 16.2 mg, 0.222 mmol, 0.1 equiv) and oxalyl chloride (265.2 µL,

2

4

.23 (s, 5H, Cp-H). The analytical data is in accordance to 422.1 mg, 3.326 mmol, 1.5 equiv). After the removal of all

36

literature.

volatiles, the residue was dissolved in CH Cl (10.0 mL), Et N

2

3

(921.9 µL,

673.0 mg,

6.651 mmol,

3.0 equiv)

and

This journal is © The Royal Society of Chemistry 20xx

J. Name., 2013, 00, 1-3 | 15

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Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Page 16 of 25

ARTICLE

Journal Name

2

-aminoethanol (173.4 µL, 176.0 mg, 2.882 mmol, 1.3 equiv) (2.2 mL, 226.9 mg, 3.543 mmol, 1.5 equiv, 1.6M in hexane) at

View Article Online

DOI: 10.1039/C8DT00109J

was added. Then Et N (921.9 µL, 673.0 mg, 6.651 mmol,

78 °C. After 2h methyl iodide (294.1 µL, 670.6 mg,

3

4

.0 equiv) and mesyl chloride (343.2 µL, 507.9 mg, 4.724 mmol, 2.0 equiv) was added at room temperature.

.434 mmol, 2.0 equiv) were added. Column chromatography Column chromatography (silica gel, PE/EE = 6:1) afforded the

(

silica gel, PE/EE = 2:1 to EE/ CH Cl = 1:1) afforded the product product as orange solid (660.2 mg, 2.121 mmol, 90%).

2 2

1

as orange solid (528.6 mg, 2.072 mmol, 94%). C H FeNO: C H FeNO: MW: 311.21 g/mol. MP: 52 °C. H-NMR (500 MHz,

MW: 255.10 g/mol. H-NMR (400 MHz, CDCl , 25 °C): δ = 4.76- CDCl , 25 °C): δ = 4.62-4.57 (m, 1H, Cp-H), 4.28-4.21 (m, 2H,

13

17 21

1

3

4

.73 (m, 2H, Cp-H), 4.35-4.33 (m, 2H, Cp-H), 4.34 (t, J = 9.4, 2H, OCH CHN, Cp-H), 4.18-4.14 (m, 1H, Cp-H), 4.10 (s, 5H, Cp-H),

2

OCH CH N), 4.20 (s, 5H, Cp-H), 3.91 (t, J = 9.4, 2H, OCH CH N). 4.08-4.03 (m, 1H, OCH CHN), 4.03-3.96 (m, 1H, OCH CHN),

2

26

The analytical data is in accordance to literature.

2.28 (s, 3H, CH ), 1.90-1.79 (m, 1H, CH(CH ) ), 1.03 (d, J = 6.9,

3 3 2

Synthesis

ferrocene

of

(4,5-dihydro-4,4-dimethyl-2-oxazolinyl) 3H, CH(CH ) ), 0.97 (d, J = 6.9, 3H, CH(CH ) ). IR (in CDCl ):

3 2 3 2 3

(Me FO).

In

accordance

with

GP1 휈̃ = 3094, 2956, 2898, 2872, 1651, 1482, 1467, 1429, 1377,

2

ferrocenecarboxylic acid (514.0 mg, 2.234 mmol, 1.0 equiv) in 1365, 1283, 1258, 1209, 1174, 1151, 1106, 1068, 1002, 971,

CH Cl (15.0 mL) was treated with DMF (17.2 µL, 16.3 mg, 951, 897, 884, 817, 661, 546, 514, 487, 453. HRMS (ESI) m/z:

2

+

0

4

.223 mmol, 0.1 equiv) and oxalyl chloride (287.4 µL, calculated for ([M+H] ): 312.1045; found: 312.1073. The

25.4 mg, 3.352 mmol, 1.5 equiv). After the removal of all analytical data is in accordance to literature.

38

volatiles, the residue was dissolved in CH Cl (10.0 mL), Et N Synthesis of (S,S )-(4-isopropyl-4,5-dihydro-2-oxazolyl)-2-

2

3

p

(929.2 µL, 678.3 mg, 6.703 mmol, 3.0 equiv) and 2-amino-2- trimethylsilyl ferrocene (iPrFOTMS). According to GP2 the

methyl-1-propanol (258.9 mg, 2.905 mmol, 1.3 equiv) was isopropyl-oxazoline iPrFO (300.1 mg, 1.010 mmol, 1.0 equiv)

added. Then Et N (929.2 µL, 678.3 mg, 6.703 mmol, 3.0 equiv) was dissolved in toluene (10.0 mL) and TMEDA (301.0 µL,

3

and mesyl chloride (345.9 µL, 511.9 mg, 4.469 mmol, 234.8 mg, 2.020 mmol, 2.0 equiv) and treated with n-BuLi

2

.0 equiv) were added. Column chromatography (silica gel, (946.7 µL, 97.0 mg, 1.515 mmol, 1.5 equiv, 1.6M in hexane) at

PE/EE = 2:1 to 1:1) afforded the product as orange solid 78 °C. After 2h trimethylsilyl chloride (256.9 µL, 219.4 mg,

564.2 mg, 1.993 mmol, 89%). C H FeNO: MW: 283.15 g/mol. 2.020 mmol, 2.0 equiv) was added at room temperature.



(

15 17

1

H-NMR (400 MHz, CDCl , 25 °C): δ = 4.79-4.72 (m, 2H, Cp-H), Column chromatography (silica gel, PE/EE = 6:1) afforded the

3

4

.36-4.30 (m, 2H, Cp-H), 4.18 (s, 5H, Cp-H), 4.00 (s, 2H, product as orange solid (315.3 mg, 0.854 mmol, 85%).

1

OCH CN), 1.35 (s, 6H, NC(CH ) ). The analytical data is in C H FeNOSi: MW: 369.36 g/mol. H-NMR (400 MHz, CDCl ,

accordance to literature.

2

3 2

19 27

3

37

25 °C): δ = 4.91-4.87 (m, 1H, Cp-H), 4.45-4.41 (m, 1H, Cp-H),

Synthesis of (S,S )-(4-isopropyl-4,5-dihydro-2-oxazolyl)-2- 4.31-4.23 (m, 2H, OCH CHN, Cp-H), 4.18 (s, 5H, Cp-H), 4.04-

p

2

methyl ferrocene

(

S_p-iPrFOMe). With some deviations to GP2

,

3.89 (m, 2H, OCH CHN), 1.87-1.74 (m, 1H, CH(CH ) ), 1.03 (d,

2

3 2

a solution of the isopropyl oxazoline iPrFO (18.8 mg, J = 6.7, 3H, CH(CH ) ), 0.92 (d, J = 6.7, 3H, CH(CH ) ), 0.32 (s,

3

2

3 2

0

.063 mmol, 1.00 equiv) in toluene (0.6 mL) and di-tert-butyl 9H, Si(CH ) ). The analytical data is in accordance to

3 3

12a,26

diethylene glycol (51.8 mg, 0.237 mmol, 3.75 equiv) was literature.

cooled to

78 °C. n-BuLi (59.3 µL, 6.1 mg, 0.095 mmol, Synthesis of (S,R )-(4-tert-butyl-4,5-dihydro-2-oxazolyl)-2-

p

1

.50 equiv, 1.6M in hexane) was added dropwise and the methyl ferrocene (tBuFOMe). With slight deviation to GP2 the

mixture was stirred for 2h. After warming to room tertbutyl-oxazoline tBuFO (250.8 mg, 0.806 mmol, 1.0 equiv)

temperature methyl iodide (7.9 µL, 18.0 mg, 0.127 mmol, was dissolved in toluene (12.0 mL) and TMEDA (600.5 µL,

2

.00 equiv) was added, followed by further stirring for 1h. Et O 468.4 mg, 4.029 mmol, 5.0 equiv) and treated with n-BuLi

2

and saturated aqueous NaHCO solution were added. The (1.0 mL, 103.2 mg, 1.612 mmol, 2.0 equiv, 1.6M in hexane) at

3

organic layer was dried over MgSO and the solvent was



78 °C. After 2h methyl iodide (100.3 µL, 228.8 mg,

removed under reduced pressure. Column chromatography 1.612 mmol, 2.0 equiv) was added at room temperature.

silica gel, PE/EE = 6:1) afforded an orange oil as a mixture of Column chromatography (silica gel, PE/EE = 10:1) afforded the

diastereomers (dr (S,S ) : (S,R ) = 6:1, 78%). Unfortunately the product as orange solid (224.5 mg, 0.690 mmol, 86%).

4

(

P

p

2

0

additive di-tert-butyl diethylene glycol could not be removed C H FeNO: MW: 325.23 g/mol. MP: 76 °C. [α] :



213.7

1

7

21

D

1

by column chromatographie and the yield was determined via (c = 1.05 mg/mL, CH Cl ). H-NMR (400 MHz, CDCl , 25 °C):

2

3

1

H-NMR with mesitylene as internal standard. C H FeNO: δ = 4.57-4.56 (m, 1H, Cp-H), 4.25-4.24 (m, 1H, Cp-H), 4.22-4.13

1

7 21

1

MW: 311.21 g/mol. major diastereomer: H-NMR (500 MHz, (m, 3H, OCH CHN, Cp-H), 4.10 (s, 5H, Cp-H), 3.91 (dd, J = 7.4,

2

CDCl , 25 °C): δ = 4.69-4.62 (m, 1H, Cp-H), 4.31-4.20 (m, 2H, 9.8, 1H, OCH CHN), 2.30 (s, 3H, CH ), 0.99 (s, 9H, C(CH ) ).

3

2

3

3 3

+

OCH CHN, Cp-H), 4.20-4.13 (m, 1H, Cp-H), 4.10 (s, 5H, Cp-H), HRMS (ESI) m/z: calculated for ([M+H] ): 326.1202; found:

2

1

2a

4

2

3

.08-4.03 (m, 1H, OCH CHN), 4.02-3.95 (m, 1H, OCH CHN), 326.1202. The analytical data is in accordance to literature.

2 2

.24 (s, 3H, CH ), 1.88-1.79 (m, 1H, CH(CH ) ), 1.01 (d, J = 6.9, Synthesis of (4R,5S,S )-(4,5-5H-indeno[1,2-d]-4,5-dihydro-2-

H, CH(CH ) ), 0.93 (d, J = 6.9, 3H, CH(CH ) ).

3

3 2

p

oxazolyl)-2-methyl ferrocene (IndFOMe). With slight deviation

3

2

3 2

Synthesis of (S,R )-(4-isopropyl-4,5-dihydro-2-oxazolyl)-2- to GP2 the (R,S)-indanol-oxazoline IndFO (300.1 mg,

p

methyl ferrocene (iPrFOMe). According to GP2 the isopropyl- 0.874 mmol, 1.0 equiv) was dissolved in toluene (13.0 mL) and

oxazoline iPrFO (702.0 mg, 2.362 mmol, 1.0 equiv) was TMEDA (260.6 µL, 203.3 mg, 1.749 mmol, 2.0 equiv) and

dissolved in toluene (24.0 mL) and TMEDA (704.1 µL, treated with n-BuLi (819.7 µL, 84.0 mg, 1.312 mmol, 1.5 equiv,

5

49.2 mg, 4.724 mmol, 2.0 equiv) and treated with n-BuLi 1.6M in hexane) at 78 °C. After 2h methyl iodide (108.9 µL,

1

6 | J. Name., 2012, 00, 1-3

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Page 17 of 25

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Journal Name

ARTICLE

2

48.2 mg, 1.749 mmol, 2.0 equiv) was added at room 1H, Cp-H), 4.19-4.16 (m, 1H, Cp-H), 4.11 (s, 5H, Cp-H ), 3.96-

View Article Online

DOI: 10.1039/C8DT00109J

temperature. Column chromatography (silica gel, PE/EE = 6:1) 3.88 (m, 2H, OCH CH N), 2.27 (s, 3H, CH ). The analytical data

afforded the product as orange solid (284.1 mg, 0.795 mmol, is in accordance to literature.

9

2

3

39

20

1%). C H FeNO: MW: 357.23 g/mol. MP: 97 °C. [α] : 236.4 Synthesis of rac-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)-2-

21 19 D

1

(c = 1.13 mg/mL, CH Cl ). H-NMR (400 MHz, CDCl , 25 °C): methyl ferrocene (Me FOMe). According to GP2 the dimethyl-

2 2 3 2

δ = 7.58-7.55 (m, 1H, Ar-H), 7.30-7.23 (m, 3H, Ar-H), 5.61 (d, oxazoline Me FO (173.2 mg, 0.612 mmol, 1.0 equiv) was

2

J = 7.3, 1H, NCH), 5.33-5.29 (m, 1H, OCH), 4.62-4.60 (m, 1H, Cp- dissolved in toluene (6.1 mL) and TMEDA (182.3 µL, 142.2 mg,

H), 4.20-4.19 (m, 1H, Cp-H), 4.13 (t, J = 2.5, 1H, Cp-H), 3.85 (s, 1.223 mmol, 2.0 equiv) and treated with n-BuLi (573.5 µL,

5

1

H, Cp-H), 3.48 (dd, J = 6.2, 17.5, 1H, CH ), 3.35 (d, J = 17.5, 58.8 mg, 0.918 mmol, 1.5 equiv, 1.6M in hexane) at



78 °C.

2

1

3

H, CH ), 2.25 (s, 3H, CH ). C-NMR (100 MHz, CDCl , 25 °C): After 2h methyl iodide (76.2 µL, 173.6 mg, 1.223 mmol,

2

3

δ = 167.1 (1C, C=N), 142.9 (1C, Ar-C), 139.6 (1C, Ar-C), 128.4 2.0 equiv) was added at room temperature. Column

1C, Ar-C), 127.6 (1C, Ar-C), 125.7 (1C, Ar-C), 125.4 (1C, Ar-C), chromatography (silica gel, PE/EE = 2:1) afforded the product

(

8

7

5.9 (1C, Cp-C), 82.1 (1C, OCH), 76.9 (1C, NCH), 72.6 (1C, Cp-C), as orange solid (170.6 mg, 0.574 mmol, 94%). C H FeNO:

16 19

0.2 (5C, Cp-C), 69.5 (1C, Cp-C), 68.9 (1C, Cp-C), 68.2 (1C, Cp- MW: 297.18 g/mol. MP: 83 °C. H-NMR (400 MHz, CDCl₃,

1

C), 39.9 (1C, CH ), 14.9 (1C, CH ). IR (in CD Cl ): 휈̃ = 3076, 2947, 25 °C): δ = 4.68-4.64 (m, 1H, Cp-H), 4.24-4.20 (m, 1H, Cp-H),

2

3

2

1

919, 1642, 1477, 1460, 1427, 1377, 1286, 1246, 1200, 1171, 4.18-4.15 (m, 1H, Cp-H), 4.10 (s, 5H, Cp-H), 3.99 (s, 2H,

106, 1068, 1015, 963, 812, 748, 729, 628, 491, 464, 449. OCH CN), 2.25 (s, CH ), 1.354 (s, 3H, NC(CH ) ), 1.349 (s, 3H,

2

3

3 2



HRMS (ESI) m/z: calculated for ([MH] ): 358.0889; found: NC(CH ) ). IR (in CDCl ): 휈̃ = 2962, 2925, 1648, 1462, 1428,

3 2 3

3

58.0891.

1377, 1363, 1287, 1199, 1106, 1063, 1016, 970, 816, 522, 494,

40

Synthesis of (4R,5R,S )-(4,5-diphenyl-4,5-dihydro-2-oxazolyl)- 468. The analytical data are in accordance to literature.

p

2

-methyl ferrocene (Ph FOMe). According to GP2 the (R,R)- Synthesis of (S)-(4-isopropyl-4,5-dihydro-2-oxazolyl)-2,5-

2

diphenyl-oxazoline Ph FO (18.6 mg, 0.046 mmol, 1.0 equiv) dimethyl ferrocene (iPrFOMe₂). According to GP3 the

2

was dissolved in toluene (0.7 mL) and TMEDA (13.6 µL, methylated

isopropyl-oxazoline

iPrFOMe

(12.0 mg,

1

0.6 mg, 0.091 mmol, 2.0 equiv) and treated with n-BuLi 0.039 mmol, 1.0 equiv) was dissolved in Et O (0.4 mL) and

2

(



2

42.8 µL, 4.4 mg, 0.068 mmol, 1.5 equiv, 1.6M in hexane) at treated with t-BuLi (23.8 µL, 2.6 mg, 0.040 mmol, 1.1 equiv,

78 °C. After 2h methyl iodide (5.7 µL, 13.0 mg, 0.091 mmol, 1.7M in pentane). After 30 min at 0 °C methyl iodide (4.8 µL,

.0 equiv) was added at room temperature. Column 10.9 mg, 0.077 mmol, 2.0 equiv) was added. Column

chromatography (silica gel, PE/EE = 6:1) afforded the product chromatography (silica gel, PE/EE = 6:1) afforded the product

as orange solid (18.9 mg, 0.045 mmol, 98%). C H FeNO: MW: as orange oil (11.0 mg, 0.034 mmol, 87%). C H FeNO: MW:

2

6

23

17 21

2

0

20

1

4

21.32 g/mol. MP: 110 °C. [α] : 10.6 (c = 1.00 mg/mL, 325.23 g/mol. [α]_D: 156.0 (c = 1.93 mg/mL, CH Cl ). H-NMR

D 2 2

CH Cl ). H-NMR (500 MHz, CDCl , 25 °C): δ = 7.44-7.31 (m, (500 MHz, CDCl , 25 °C): δ = 4.26 (dd, J = 8.2, 9.5, 1H,

1

2

3

1

0H, Ph-H), 5.30 (d, J = 6.9, 1H, OCHPh), 5.12 (d, J = 6.9, 1H, OCH CHN), 4.10-4.08 (m, 2H, Cp-H), 4.07-4.06 (m, 1H,

2

NCHPh), 4.82-4.81 (m, 1H, Cp-H), 4.36-4.35 (m, 1H, Cp-H), 4.27 OCH CHN), 4.02 (s, 5H, Cp-H), 4.02-3.98 (m, 1H, OCH CHN),

2

13

(

t, J = 2.5, 1H, Cp-H), 4.21 (s, 5H, Cp-H), 2.39 (s, 3H, CH₃). C- 2.20 (s, 3H, CH ), 2.16 (s, 3H, CH ), 1.90-1.80 (m, 1H, CH(CH ) ),

3 3 3 2

NMR (125 MHz, CDCl , 25 °C): δ = 167.5 (1C, C=N), 142.9 (1C, 1.03 (d, J = 6.9, 3H, CH(CH ) ), 0.97 (d, J = 6.9, 3H, CH(CH ) ).

3

3 2

13

Ph-C), 141.1 (1C, Ph-C), 129.0 (2C, Ph-C), 129.0 (2C, Ph-C),

C-NMR (125 MHz, CDCl , 25 °C): δ = 166.2 (1C, C=N), 85.5 (1C,

3

1

28.4 (1C, Ph-C), 127.7 (1C, Ph-C), 126.7 (2C, Ph-C), 125.8 (2C, Cp-C), 85.2 (1C, Cp-C), 72.3 (1C, NCH), 70.8 (5C, Cp-C), 70.2 (1C,

Ph-C), 88.1 (1C, OCH), 85.9 (1C, Cp-C), 79.1 (1C, NCH), 72.9 (1C, Cp-C), 70.0 (1C, Cp-C), 69.9 (1C, Cp-C), 68.8 (1C, OCH ), 32.7

2

Cp-C), 70.4 (5C, Cp-C), 69.9 (1C, Cp-C), 69.1 (1C, Cp-C), 68.5 (1C, CH(CH ) ), 18.9 (1C, CH(CH ) ), 18.1 (1C, CH(CH ) ), 15.2

3

2

3 2

(

1C, Cp-C), 15.2 (CH ). IR (in CDCl ): 휈̃ = 3086, 3063, 3029, (1C, CH ), 14.9 (1C, CH ). IR (in CDCl ): 휈̃ = 3092, 2955, 2897,

3 3 3 3 3

2

1

8

919, 1644, 1603, 1584, 1494, 1475, 1453, 1428, 1377, 1350, 1643, 1466, 1417, 1377, 1337, 1305, 1266, 1218, 1195, 1106,

277, 1231, 1209, 1172, 1149, 1106, 1066, 1011, 970, 910, 1061, 1027, 1008, 969, 909, 886, 814, 731, 586, 527, 496, 422.



83, 818, 759, 732, 697, 663, 651, 624, 585, 536, 488, 455. HRMS (ESI) m/z: calculated for ([M



Na] ): 348.1021;



HRMS (ESI) m/z: calculated for

44.1022.

Synthesis of rac-(4,5-dihydro-2-oxazolyl)-2-methyl ferrocene trimethylsilyl-5-methyl ferrocene (iPrFOTMSMe). According



M+Na



: 444.1016, found: found: 348.1013.

4

Synthesis of (S,S )-(4-isopropyl-4,5-dihydro-2-oxazolyl)-2-

p

(

H FOMe). According to GP2 the oxazolinyl ferrocene H FO to GP3 the TMS-isopropyl-oxazoline iPrFOTMS (89.3 mg,

2

170.6 mg, 0.669 mmol, 1.0 equiv) was dissolved in toluene 0.242 mmol, 1.0 equiv) was dissolved in Et O (2.4 mL) and

2

6.6 mL) and TMEDA (199.3 µL, 155.5 mg, 1.338 mmol, treated with t-BuLi (149.3 µL, 16.3 mg, 0.254 mmol, 1.1 equiv,

2

1

.0 equiv) and treated with n-BuLi (627.0 µL, 64.3 mg, 1.7M in pentane). After 30 min at 0 °C methyl iodide (30.1 µL,

.003 mmol, 1.5 equiv, 1.6M in hexane) at 78 °C. After 2h 68.6 mg, 0.484 mmol, 2.0 equiv) was added. Column



methyl iodide (83.3 µL, 189.8 mg, 1.338 mmol, 2.0 equiv) was chromatography (silica gel, PE/EE = 10:1) afforded the product

added at room temperature. Column chromatography (silica as orange oil (72.6 mg, 0.189 mmol, 78%). C H FeNOSi: MW:

2

0 29

20

1

gel, PE/EE = 1:1) afforded the product as orange solid 383.39 g/mol. [α]_D: 15.2 (c = 1.80 mg/mL, CH Cl ). H-NMR

2

(

132.5 mg, 0.492 mmol, 74%). C H FeNO: MW: 269.13 g/mol. (400 MHz, CDCl , 25 °C): δ = 4.34 (d, J = 2.3, 1H, Cp-H), 4.27

14 15 3

1

MP: 54 °C. H-NMR (400 MHz, CDCl , 25 °C): δ = 4.65-4.61 (m, (dd, J = 7.5, 8.7, 1H, OCH CHN), 4.11 (s, 5H, Cp-H), 4.09 (d, J =

3

2

1

H, Cp-H), 4.31 (dt, J = 2.5, 9.4, 2H, OCH CH N), 4.26-4.23 (m, 2.3, 1H, Cp-H), 4.01-3.90 (m, 2H, OCH CHN), 2.25 (s, 3H, CH ),

2 2 2 3

This journal is © The Royal Society of Chemistry 20xx

J. Name., 2013, 00, 1-3 | 17

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Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Page 18 of 25

ARTICLE

Journal Name

1

0

.83-1.74 (m, 1H, CH(CH ) ), 1.04 (d, J = 6.6, 3H, CH(CH ) ), Synthesis of (4R,5R)-(4,5-diphenyl-4,5-dihydro-2-oxazolyl)-

3 2 3 2

View Article Online

1

3

DOI: 10.1039/C8DT00109J

.91 (d, J = 6.6, 3H, CH(CH ) ), 0.28 (s, 9H, Si(CH ) ). C-NMR 2,5-dimethyl ferrocene (Ph FOMe ). According to GP3 the

3

2

3 3

2

(

100 MHz, CDCl , 25 °C): δ = 168.1 (1C, C=N), 89.4 (1C, Cp-C), methylated (R,R)-diphenyl-oxazoline Ph FOMe (39.6 mg,

3

2

7

5.6 (1C, Cp-C), 74.6 (1C, Cp-C), 74.1 (1C, Cp-C), 73.3 (1C, NCH), 0.094 mmol, 1.0 equiv) was dissolved in Et O (1.4 mL) and

2

2.7 (1C, Cp-C), 70.4 (5C, Cp-C), 69.4 (1C, OCH ), 33.0 (1C, treated with t-BuLi (60.8 µL, 6.6 mg, 0.103 mmol, 1.1 equiv,

2

CH(CH ) ), 19.5 (1C, CH(CH ) ), 18.4 (1C, CH(CH ) ), 14.7 (1C, 1.7M in pentane). After 15 min at 0 °C methyl iodide (11.7 µL,

3

2

3 2

CH ), 0.7 (3C, Si(CH ) ). IR (in CDCl ): 휈̃ = 3093, 2955, 2896, 26.7 mg, 0.188 mmol, 2.0 equiv) was added. Column

3

3 3

3

1

649, 1464, 1414, 1387, 1315, 1243, 1191, 1146, 1107, 1063, chromatography (silica gel, PE/EE = 10:1) afforded the product

027, 1002, 981, 937, 886, 838, 815, 756, 693, 628, 500. HRMS as red solid (30.6 mg, 0.070 mmol, 75%). C H FeNO: MW:

19 25



20

1

(ESI) m/z: calculated for ([M



H] ): 384.1441; found: 384.1414.

435.34 g/mol. [α]_D: 65.8 (c = 1.00 mg/mL, CH Cl ). H-NMR

2 2

Synthesis of (S)-(4-tert-butyl-4,5-dihydro-2-oxazolyl)-2,5- (400 MHz, CDCl , 25 °C): δ = 7.48-7.31 (m, 10H, Ph-H), 5.30 (d,

3

dimethyl ferrocene (tBuFOMe₂). According to GP3 the J = 7.1, 1H, OCHPh), 5.14 (d, J = 7.1, 1H, NCHPh), 4.22-4.17 (m,

methylated

tert-butyl-oxazoline

tBuFOMe

(9.3 mg, 2H, Cp-H), 4.14 (s, 5H, Cp-H), 2.32 (s, 3H, CH ), 2.30 (s, 3H,

3

13

0

.029 mmol, 1.0 equiv) was dissolved in Et O (0.4 mL) and CH₃). C-NMR (125 MHz, CDCl , 25 °C): δ = 167.8 (1C, C=N),

2

3

treated with t-BuLi (20.2 µL, 2.2 mg, 0.034 mmol, 1.2 equiv, 143.0 (1C, Ph-C), 141.4 (1C, Ph-C), 129.0 (2C, Ph-C), 128.9 (2C,

1

8

.7M in pentane). After 30 min at 0 °C methyl iodide (3.6 µL, Ph-C), 128.4 (1C, Ph-C), 127.7 (1C, Ph-C), 126.7 (2C, Ph-C),

.1 mg, 0.057 mmol, 2.0 equiv) was added. Column 125.8 (2C, Ph-C), 88.0 (1C, OCH), 86.1 (1C, Cp-C), 85.7 (1C, Cp-

chromatography (silica gel, PE/EE = 20:1) afforded the product C), 78.9 (1C, NCH), 71.0 (5C, Cp-C), 70.5 (1C, Cp-C), 69.3 (1C,

as orange oil (8.6 mg, 0.025 mmol, 89%). C H FeNO: MW: Cp-C), 15.6 (1C, CH ), 15.4 (1C, CH ). IR (film): 휈̃ = 3063, 3029,

1

9

25

3

20

1

3

39.25 g/mol. [α]_D

: 182.1 (c = 1.00 mg/mL, CH Cl ). H-NMR 2919, 1636, 1603, 1583, 1493, 1486, 1452, 1416, 1377, 1304,

2 2

(

500 MHz, CDCl , 25 °C): δ = 4.24-4.16 (m, 2H, OCH CHN), 4.10 1243, 1212, 1190, 1105, 1061, 1017, 1001, 968, 909, 882, 814,

3

2

d, J = 1.9, 1H, Cp-H), 4.05 (d, J = 1.9, 1H, Cp-H), 4.02 (s, 5H, Cp- 758, 731,696, 654, 626, 585, 535, 491, 464. HRMS (ESI) m/z:



H), 3.90 (dd, J = 7.3, 9.8, 1H, OCH CHN), 2.22 (s, 3H, CH ), 2.15 calculated for ([M] ): 436.1359; found: 436.1331.

2

3

1

3

5

(s, 3H, CH ), 0.99 (s, 9H, tBu). C-NMR (125 MHz, CDCl , 25 °C): Synthesis of bis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'-dihydro-2'-

3

p

δ = 166.2 (1C, C=N), 85.6 (1C, Cp-C), 85.1 (1C, Cp-C), 76.0 (1C, oxazolyl-κN)-cyclopentadienyl-κC)(η5-cyclopentadienyl)

NCH), 70.8 (5C, Cp-C), 70.3 (1C, Cp-C), 70.0 (1C, Cp-C), 69.8 (1C, ferrocene]] digold(I) ((R )-iPrFOAu(I)). The isopropyl-oxazoline

p

Cp-C), 67.6 (1C, OCH ), 33.9 (1C, C(CH ) ), 26.0 (3C, C(CH ) ), iPrFO (19.8 mg, 0.067 mmol, 1.0 equiv) and di-tert-

2

3 3

1

2

1

7

5.4 (1C, CH ), 14.8 (1C, CH ). IR (film): 휈̃ = 3093, 2950, 2900, butyldiethyleneglycol

867, 1644, 1478, 1417, 1392, 1377, 1363, 1305, 1280, 1219, 3.3 equiv) were dissolved in toluene (0.7 mL) and treated with

193, 1105, 1072, 1053, 1025, 1009, 965, 947, 889, 814, 747, n-BuLi (54.1 µL, 5.5 mg, 0.087 mmol, 1.3 equiv, 1.6M in

(51.9 µL,

47.3 mg,

0.216 mmol,

3

18, 617, 587, 539, 497, 424. HRMS (ESI) m/z: calculated for hexane) at



78 °C. After 2 h the reaction mixture was warmed



([MNa] ): 340.1353; found: 340.1358.

to room temperature and chloro(dimethyl sulfide)gold(I)

Synthesis of (4R,5S)-(4,5-5H-indeno[1,2-d]-4,5-dihydro-2- (19.6 mg, 0.067 mmol, 1.0 equiv) was added. The reaction

oxazolyl)-2,5-dimethyl ferrocene (IndFOMe₂). According to mixture was stirred overnight, then filtered over celite with

GP3 the methylated (R,S)-indanol-oxazoline IndFOMe CH Cl . The crude product was purified by column

2

(

19.2 mg, 0.054 mmol, 1.0 equiv) was dissolved in Et O chromatography (silica gel, PE/EE = 6:1). The product was

2

(

0.8 mL) and treated with t-BuLi (34.8 µL, 3.8 mg, 0.059 mmol, isolated as a mixture of (R ,R )-, (S ,S )- and (R ,S )-isomers

p

1

.1 equiv, 1.7M in pentane). After 15 min at 0 °C methyl iodide (13.7 mg, 0.014 mmol, 42%) with a ratio of 7.0:1.0:2.7. The

(

6.7 µL, 15.3 mg, 0.107 mmol, 2.0 equiv) was added. Column main product, the (R ,R )-isomer could be crystallized from

p p

1

chromatography (silica gel, PE/EE = 6:1) afforded the product CH Cl /pentane and its H NMR signals could be assigned.

as red solid (13.7 mg, 0.037 mmol, 69%). C H FeNO: MW: C H Au Fe N O : MW: 986.28 g/mol. H-NMR (400 MHz,

3

2

1

22

21

32 36

2

2 2 2

20

71.26 g/mol. MP: 92 °C. [α] : 286.8 (c = 1.13 mg/mL, CDCl , 25 °C): δ = 4.83-4.80 (m, 2H, Cp-H), 4.50 (t, J = 2.5, 2H,

D 3

1

CH Cl ). H-NMR (400 MHz, CDCl , 25 °C): δ = 7.59-7.53 (m, 1H, Cp-H), 4.42-4.33 (m, 6H, Cp-H, OCH CHN), 4.40 (s, 10H, Cp-H),

2

3

2

Ar-H), 7.32-7.23 (m, 3H, Ar-H), 5.62 (d, J = 7.3, 1H, NCH), 5.37- 4.25 (dd, J = 4.8, 7.6, 2H, OCH CHN), 2.51-2.42 (m, 2H,

2

5

3

.31 (m, 1H, OCH), 4.06-4.03 (m, 2H, Cp-H), 3.82 (s, 5H, Cp-H), CH(CH ) ), 0.88 (d, J = 7.0, 6H, CH(CH ) ), 0.80 (d, J = 7.0, 6H,

3 2 3 2

.50 (dd, J = 6.4, 17.6, 1H, CH ), 3.37 (d, J = 17.6, 1H, CH ), 2.18 CH(CH ) ). IR (in CH Cl ): 휈̃ = 2924, 1613, 1432, 1378, 1229,

2

3 2

2

13



(s, 3H, CH ), 2.15 (s, 3H, CH ). C-NMR (100 MHz, CDCl₃, 1158, 979, 485, 420. HRMS (ESI) m/z: calculated for ([M



Na] ):

3

2

1

5 °C): δ = 167.3 (1C, C=N), 143.1 (1C, Ar-C), 139.6 (1C, Ar-C), 1009.0700; found: 1009.0680.

5

28.4 (1C, Ar-C), 127.6 (1C, Ar-C), 125.7 (1C, Ar-C), 125.4 (1C, Synthesis of bis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'-dihydro-2'-

p

5

Ar-C), 85.7 (1C-Cp-C), 85.6 (1C-Cp-C), 81.9 (1C, OCH) 76.6 (1C, oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

NCH), 70.8 (5C-Cp-C), 70.21 (1C-Cp-C), 70.19 (1C-Cp-C), 69.2 cyclopentadienyl) ferrocene]] digold(I) (iPrFOMeAu(I)).

(

1C-Cp-C), 40.0 (1C, CH ), 15.3 (1C, CH ), 15.2 (1C, CH ). IR (in According to GP4 the methylated isopropyl-oxazoline iPrFOMe

2 3 3

CDCl₃): 휈̃ = 3090, 3073, 3039, 3025, 2949, 2919, 1725, 1632, (300.0 mg, 0.964 mmol, 1.0 equiv) was dissolved in Et O

2

1

4

460, 1416, 1377, 1301, 1260, 1214, 1194, 1168, 1105, 1064, (9.6 mL) and treated with t-BuLi (595.4 µL, 64.8 mg,

023, 1000, 859, 814, 748, 733, 631, 587, 551, 495, 469, 1.012 mmol, 1.1 equiv, 1.7M in pentane). After 30 min at 0 °C



48,419. HRMS (ESI) m/z: calculated for ([M



H] ): 372.1045; chloro(dimethyl sulfide)gold(I) (255.5 mg, 0.868 mmol,

0.9 equiv) and toluene (4.8 mL) were added. Washing 3 times

found: 372.1064.

1

8 | J. Name., 2012, 00, 1-3

This journal is © The Royal Society of Chemistry 20xx

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Page 19 of 25

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Journal Name

ARTICLE

with pentane afforded the product as red solid (385.8 mg, (500 MHz, CD Cl , 25 °C): δ = 4.51-4.43 (m, 4H, OC H CHN), 4.34

2

View Article Online

2

0

.380 mmol, 88%) based on chloro(dimethyl sulfide)gold(I). (d, J = 2.5, 2H, Cp-H), 4.20 (s, 10H, Cp-H)^D, ^O4.^I1^:¹2⁰^.(¹d⁰d³⁹,^/J^C=⁸^D5^T.7⁰⁰, ¹9⁰.⁹5^J,

C H Au Fe N O : MW: 1014.33 g/mol. MP: >190 °C 2H, OCH CHN), 4.09 (d, J = 2.5, 2H, Cp-H), 2.19 (s, 6H, CH ),

34

40

2

0

2

3

2

1

13

(decomp.). [α]_D: 1520.1 (c = 1.00 mg/mL, CH Cl ). H-NMR 1.13 (s, 18H, C(CH₃)₃). C-NMR (125 MHz, CD Cl , 25 °C): δ =

2

(

700 MHz, C D , 25 °C): δ = 4.60 (d, J = 1.7, 2H, Cp-H), 4.54 (s, 180.1 (2C, C=N), 87.7 (2C, Cp-C), 86.0 (2C, Cp-C), 79.7 (2C, Cp-

6 6

1

0H, Cp-H), 4.38 (d, J = 1.7, 2H, Cp-H), 3.89-3.85 (m, 2H, C), 76.0 (2C, NCH), 75.9 (2C, Cp-C), 72.3 (2C, Cp-C), 71.1 (10C,

OCH CHN), 3.64 (dd, J = 6.2, 8.8, 2H, OCH CHN), 3.58 Cp-C), 69.9 (2C, OCH ), 34.3 (2C, C(CH ) ), 26.8 (6C, C(CH ) ),

2

3 3

(

dd, J = 8.8, 9.9, 2H, OCH CHN), 2.48-2.41 (m, 2H, CH(CH ) ), 16.4 (2C, CH ). IR (in CH Cl ): 휈̃ = 2954, 2867, 1586, 1473, 1443,

2 3 2 3 2 2

0

.77 (d, J = 6.9, 6H, CH(CH ) ), 0.50 (d, J = 6.9, 6H, CH(CH ) ). 1405, 1396, 1378, 1367, 1312, 1257, 1186, 1143, 1105, 1087,

3 2 3 2

1

3

C-NMR (175 MHz, C D , 25 °C): δ = 179.4 (2C, C=N), 89.6 (2C, 1034, 998, 969, 922, 813, 736, 501, 480. HRMS (ESI) m/z:

6

Cp-C), 85.6 (2C, Cp-C), 80.3 (2C, Cp-C), 76.1 (2C, Cp-C), 71.8 calculated for ([M]): 1042.1429; found: 1042.1418.

5

(

3

2C, Cp-C), 71.50 (2C, NCH), 71.46 (10C, Cp-C), 67.6 (2C, OCH₂), Synthesis of bis[µ-[(η -(S,S )-2-(4',5'-5'H-Indeno[1,2-d]-4',5'-

p

5

1.6 (2C, CH(CH ) ), 18.1 (2C, CH(CH ) ), 17.0 (2C, CH ), 15.1 dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

3 2 3 2 3

(

2C, CH(CH ) ). IR (in CH Cl ): 휈̃ = 3080, 2956, 2920, 2868, 1604, cyclopentadienyl) ferrocene]] digold(I) (IndFOMeAu(I)).

3 2 2 2

1

6

477, 1463, 1442, 1407, 1387, 1321, 1302, 1276, 1254, 1186, According to GP4 the methylated (R,S)-indanol-oxazoline

146, 1106, 1082, 1052, 1029, 1000, 964, 918, 814, 734, 679, IndFOMe (59.1 mg, 0.165 mmol, 1.0 equiv) was dissolved in

16, 559, 491, 463, 448, 418. HRMS (ESI) m/z: calculated for Et O (1.7 mL) and treated with t-BuLi (107.0 µL, 11.7 mg,

2

(

[M]): 1014.1115; found: 1014.1110.

0.182 mmol, 1.1 equiv, 1.7M in pentane). After 15 min at 0 °C

Synthesis of bis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'-dihydro-2'- chloro(dimethyl sulfide)gold(I) (34.1 mg, 0.116 mmol,

0.7 equiv) and toluene (0.8 mL) were added. Washing 3 times

5

p

5

oxazolyl-κN)-3-trimethylsilyl-cyclopentadienyl-κC)(η -

cyclopentadienyl) ferrocene]] digold(I) (iPrFOTMSAu(I)). with pentane afforded the product as orange solid (53.3 mg,

According to GP4 the TMS-isopropyl-oxazoline iPrFOTMS 0.048 mmol, 83%) based on chloro(dimethyl sulfide)gold(I).

(

90.0 mg, 0.244 mmol, 1.0 equiv) was dissolved in Et O C H Au Fe N O : MW: 1106.39 g/mol. MP: >165 °C

2 42 36 2 2 2 2

20

1

(2.4 mL) and treated with t-BuLi (150.5 µL, 16.4 mg, (decomp.). [α]_D

: 986.0 (c = 1.07 mg/mL, CH Cl ). H-NMR

2 2

0

.256 mmol, 1.1 equiv, 1.7M in pentane). After 30 min at 0 °C (700 MHz, CDCl , 25 °C): δ = 8.01 (d, J = 7.8, 2H, Ar-H), 7.26-

3

chloro(dimethyl

.8 equiv) and toluene (1.2 mL) were added. Washing 3 times NCH), 5.60-5.58 (m, 2H, OCH), 4.36 (d, J = 2.4, 2H, Cp-H), 4.31

with pentane afforded the product as orange solid (79.4 mg, (s, 10H, Cp-H), 4.21 (d, J = 2.4, 2H, Cp-H), 3.51 (dd, J = 6.7, 17.7,

sulfide)gold(I)

(57.4 mg,

0.195 mmol, 7.22 (m, 4H, Ar-H), 7.01-6.98 (m, 2H, Ar-H), 5.82 (d, J = 7.8, 2H,

0

13

0

.070 mmol, 72%) based on chloro(dimethyl sulfide)gold(I). 2H, CH ), 3.39 (d, J = 17.7, 2H, CH ), 2.22 (s, 6H, CH ). C-NMR

2 2 3

C H Au Fe N O Si : MW: 1130.64 g/mol. MP: >200 °C (175 MHz, CDCl , 25 °C): δ = 178.9 (2C, C=N), 140.3 (2C, Ar-C),

3

8

52

2

3

20

1

(

decomp.). [α]_D: 1468.1 (c = 0.14 g/dL, CH Cl ). H-NMR (500 139.4 (2C, Ar-C), 129.1 (2C, Ar-C), 127.9 (2C, Ar-C), 127.3 (2C,

2 2

MHz, CD Cl , 25 °C): δ = 4.48 (d, J = 2.5, 2H, Cp-H), 4.42 (d, Ar-C), 125.0 (2C, Ar-C), 87.7 (2C, Cp-C), 84.7 (2C, OCH), 83.7

2

J = 2.5, 2H, Cp-H), 4.40 (s, 10H, Cp-H), 4.35 (dd, J = 3.2, 6.9, 2H, (2C, Cp-C), 79.9 2C, NCH), 77.2 (2C, Cp-C), 76.4 (2C, Cp-C), 71.7

OCH CHN), 4.31-4.28 (m, 4H, OCH CHN), 2.51-2.43 (m, 2H, (2C, Cp-C), 70.7 (10C, Cp-C), 39.6 (2C, CH ), 16.6 (2C, CH ). IR

2

3

CH(CH ) ), 0.88 (d, J = 6.9, 6H, CH(CH ) ), 0.80 (d, J = 6.9, 6H, (in CH Cl ): 휈̃ = 2948, 2874, 1761, 1657, 1596, 1488, 1440,

3

2

3 2

2

13

CH(CH ) ), 0.31 (s, 18H, Si(CH ) ). C-NMR (125 MHz, CD Cl , 1392, 1373, 1359, 1316, 1295, 1264, 1225, 1202, 1138, 1098,

3

2

3 3

2

8

7

5 °C): δ = 178.9 (2C, C=N), 93.8 (2C, Cp-C), 83.5 (2C, Cp-C), 1078, 1049, 1009, 975, 930, 880, 866, 824, 805, 777, 754, 723,

0.1 (2C, Cp-C), 76.4 (2C, Cp-C), 72.6 (2C, Cp-C), 72.4 (2C, NCH), 710, 662, 619, 504, 450. HRMS (ESI) m/z: calculated for ([M]):

0.7 (10C, Cp-C), 67.7 (2C, OCH ), 32.0 (2C, CH(CH ) ), 18.5 (2C, 1106.0803; found: 1106.0794

2

3 2

5

CH(CH ) ), 14.9 (2C, CH(CH ) ), 1.0 (6C, Si(CH ) ). IR (in CH Cl ): Synthesis of bis[µ-[(η -(S,S )-2-(4',5'-diphenyl-4',5'-dihydro-2'-

휈̃ = 2953, 2925, 2902, 1607, 1479, 1403, 1382, 1314, 1264, oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

3

2

3 2

3 3

2

p

5

1

7

243, 1216, 1167, 1130, 1108, 1073, 1002, 960, 872, 834, 817, cyclopentadienyl) ferrocene]] digold(I) (Ph FOMeAu(I)).

2

54, 687, 627, 489, 448. HRMS (ESI) m/z: calculated for According to GP4 the methylated (R,R)-diphenyl-oxazoline



([M



Na] ): 1153.1491; found: 1153.1492.

Ph FOMe (100.0 mg, 0.237 mmol, 1.0 equiv) was dissolved in

2

5

Synthesis of bis[µ-[(η -(S,R )-2-(4'-tert-butyl-4',5'-dihydro-2'- Et O (2.4 mL) and treated with t-BuLi (153.6 µL, 16.7 mg,

oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

p

2

5

0.261 mmol, 1.1 equiv, 1.7M in pentane). After 15 min at 0 °C

cyclopentadienyl) ferrocene]] digold(I) (tBuFOMeAu(I)). chloro(dimethyl

sulfide)gold(I)

(48.9 mg,

0.166 mmol,

According to GP4 the methylated tert-butyl-oxazoline 0.7 equiv) and toluene (1.2 mL) were added. Washing 3 times

tBuFOMe (70.3 mg, 0.216 mmol, 1.0 equiv) was dissolved in with pentane afforded the product as orange solid (77.8 mg,

Et O (2.2 mL) and treated with t-BuLi (139.9 µL, 15.2 mg, 0.063 mmol, 76%) based on chloro(dimethyl sulfide)gold(I).

2

0

.238 mmol, 1.1 equiv, 1.7M in pentane). After 30 min at 0 °C C H Au Fe N O : MW: 1234.56 g/mol. MP: 174 °C. [α]_D:

52 44 2 2 2 2

chloro(dimethyl

1

sulfide)gold(I)

(50.9 mg,

0.173 mmol,

76.7 (c = 1.05 mg/mL, CH Cl ) H-NMR (700 MHz, CD Cl ,

2 2 2 2

0

.8 equiv) and toluene (1.1 mL) were added. Washing 3 times 25 °C): δ = 7.54-7.40 (m, 20H, Ph-H), 5.41 (d, J = 8.6, 2H,

with pentane afforded the product as red solid (75.3 mg, OCHPh), 5.36 (d, J = 8.6, 2H, NCHPh), 4.35 (d, J = 2.4, 2H, Cp-H),

0

.072 mmol, 84%) based on chloro(dimethyl sulfide)gold(I). 4.22 (s, 10H, Cp-H) 4.02 (d, J = 2.4, 2H, Cp-H), 2.22 (s, 6H, CH ).

3

13

C H Au Fe N O : MW: 1042.38 g/mol. MP: >180 °C

C-NMR (175 MHz, CD Cl , 25 °C): δ = 179.8 (2C, C=N), 141.1

2 2

36

44

2

0

2

1

(decomp.). [α]_D: 1175.4 (c = 0.87 mg/mL, CH Cl ). H-NMR (2C, Ph-C), 139.0 (2C, Ph-C), 129.5 (4C, Ph-C), 129.4 (2C, Ph-C),

2 2

J. Name., 2013, 00, 1-3 | 19

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Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Page 20 of 25

ARTICLE

Journal Name

1

29.2 (4C, Ph-C), 128.7 (2C, Ph-C), 127.7 (4C, Ph-C), 126.4 (4C, H_m_a_j_o_r), 4.07 (d, J = 2.3, 2H, Cp-H_m_i_n_o_r), 4.06 (d, J =_V _i 2 _e _w .1 _A ,_r _t 2 _i _c _l H _e ,_O _n C _l _i p _n _e -

Ph-C), 89.5 (2C, OCH), 87.5 (2C, Cp-C), 86.9 (2C, Cp-C), 80.4 (2C, H_m_a_j_o_r), 2.19 (s, 6H, CH₃_,_m_i_n_o_r), 2.18 (s, 6H,^DC^OH^I^:₃¹_,⁰_m^._a¹_j⁰_o_r³ )⁹,^/1^C.⁸5^D9^T(⁰s⁰,¹6⁰H⁹^J,

NCH), 78.9 (2C, Cp-C), 76.8 (2C, Cp-C), 70.93 (10C, Cp-C), 70.92 NCCH₃_,_m_i_n_o_r), 1.58 (s, 6H, NCCH₃_,_m_a_j_o_r), 1.54 (s, 6H, NCCH₃_,_m_i_n_o_r),

13

(2C, Cp-C), 16.9 (2C, CH ). IR (in CH Cl ): 휈̃ = 2918, 1596, 1448, 1.52 (s, 6H, NCCH₃_,_m_a_j_o_r). C-NMR (175 MHz, CD Cl , 25 °C): δ =

3

2

1

4

402, 1367, 1233, 1178, 1091, 1000, 757, 698, 543, 527, 483, 177.8 (2C, C=N), 177.7 (2C, C=N), 87.8 (2C, Cp-C), 87.0 (2C, Cp-

69, 411. HRMS (ESI) m/z: calculated for ([M]): 1234.1430; C), 86.6 (2C, Cp-C), 86.3 (2C, Cp-C), 79.4 (2C, Cp-C), 79.3 (2C,

found: 1234.1412..

Synthesis of

cyclopentadienyl-κC)(η -cyclopentadienyl)

digold(I) (H FOMeAu(I)). According to GP4 the methylated (2C, NC(CH ) ), 29.2 (2C, NC(CH ) ), 28.6 (2C, NC(CH ) ), 28.5

Cp-C), 79.2 (2C, OCH ), 79.0 (2C, OCH ), 76.2 (2C, Cp-C), 75.9

rac-bis[µ-[(η -2-(2'-oxazolyl-κN)-3-methyl- (2C, Cp-C), 74.0 (2C, Cp-C), 73.1 (2C, Cp-C), 70.8 (10C, Cp-C),

2 2

5

ferrocene]] 70.7 (10C, Cp-C), 68.0 (2C, NC(CH ) ), 67.9 (2C, NC(CH ) ), 29.3

3

2

3 2

2

3 2

oxazolinyl ferrocene H FOMe (100.0 mg, 0.372 mmol, (2C, NC(CH ) ), 15.9 (2C, CH ), 15.8 (2C, CH ). IR (in CH Cl ):

2

3 2

3

2

1

.0 equiv) was dissolved in Et O (3.7 mL) and treated with t- 휈̃ = 2963, 2921, 2896, 1597, 1445, 1404, 1377, 1365, 1352,

2

BuLi (229.5 µL, 25.0 mg, 0.390 mmol, 1.1 equiv, 1.7M in 1314, 1266, 1195, 1166, 1141, 1104, 1077, 1029, 997, 970,

pentane). After 30 min at 0 °C chloro(dimethyl sulfide)gold(I) 903, 812, 735, 702, 679, 636, 534, 496, 473. HRMS (ESI) m/z:

(

87.6 mg, 0.297 mmol, 0.8 equiv) and toluene (1.9 mL) were calculated for ([M]): 986.0802; found: 986.0802.

5

added. Washing 3 times with pentane afforded the product as Synthesis

brown solid (95.2 mg, 0.102 mmol, 69%) based on cyclopentadienyl-κC)(η -cyclopentadienyl)

chloro(dimethyl sulfide)gold(I). The enantiomers (R ,R ), (S ,S ) digold(I) (H FOAu(I)). The oxazolinyl ferrocene H FO (99.0 mg,

of

rac-bis[µ-[(η -2-(2'-oxazolyl-κN)-

5

ferrocene]]

p

2

and their diastereomer (S ,R ) were formed in a dr = 1:1.8, but 0.388 mmol, 1.0 equiv) was dissolved in toluene (3.8 mL) and

p

the ratio could not be assigned to the individual TMEDA (115.7 µL, 90.2 mg, 0.776 mmol, 2.0 equiv) and treated

diastereomers. Due to fast decomposition in solution, the with n-BuLi (291.1 µL, 29.8 mg, 0.466 mmol, 1.2 equiv, 1.6M in

NMR spectra for this compound show impurities, especially hexane) at 78 °C. After 2h the reaction mixture was warmed

1

the H-NMR spectrum is relatively complex. C H Au Fe N O : to room temperature and chloro(dimethyl sulfide)gold(I)

28

1

2

2 2 2

MW: 930.17 g/mol. MP: >169 °C (decomp.). H-NMR (400 (114.3 mg, 0.388 mmol, 1.0 equiv) was added. The reaction

MHz, CDCl , 25 °C): δ = 4.60-4.46 (m, 8H, OCH_m_i_n_o_r, OCH_m_a_j_o_r), mixture was stirred overnight, filtered over celite with CH Cl₂

3

2

4

.37 (d, J = 2.1, 2H, Cp-H_m_i_n_o_r), 4.33 (d, J = 2.1, 2H, Cp-H_m_a_j_o_r), and washed pentane and acetone to yield the product as

.30-4.07 (m, 8H, NCH_m_i_n_o_r, NCH_m_a_j_o_r), 4.25 (s, 10H, Cp-H_m_i_n_o_r), brown solid (106.7 mg, 0.118 mmol, 61%). The enantiomers

.15 (s, 10H, Cp-H_m_a_j_o_r), 2.20 (s, 6H, CH₃_,_m_i_n_o_r), 2.19 (s, 6H, (R ,R ), (S ,S ) and their diastereomer (S ,R ) were formed in a

p

13

CH₃_,_m_a_j_o_r). C-NMR (175 MHz, CD Cl , 25 °C): δ = 179.9 (2C, dr = 1:1.2, but the ratio cannot be assigned to the

2

C=N), 179,8 (2C, C=N), 87.6 (2C, Cp-C), 87.4 (2C, Cp-C), 84.9 disastereomers. Due to fast decomposition in solution, the

(

2C, Cp-C), 84.3 (2C, Cp-C), 79.8 (2C, OCH ), 79.5 (2C, OCH ), NMR spectra for this compound show impurities.

2 2

7

6.3 (2C, Cp-C), 76.1 (2C, Cp-C), 73.2 (2C, Cp-C), 72.0 (2C, Cp- C H Au Fe N O : MW: 902.11 g/mol. MP: >158 °C (decomp.).

26 24 2 2 2 2

1

C), 70.9 (10C, Cp-C), 70.7 (10C, Cp-C), 68.3 (2C, Cp-C), 68.2 (2C, H-NMR (700 MHz, CD Cl , 25 °C): δ = 4.87-4.86 (m, 2H, Cp-

2

Cp-C), 56.3 (2C, NCH ), 56.2 (2C, NCH ), 16.3 (2C, CH ), 16.2 H_m_i_n_o_r), 4.85-4.84 (m, 2H, Cp-H_m_a_j_o_r), 4.54-4.48 (m, 4H,

2

3

(

2C, CH ). IR (in CH Cl ): 휈̃ = 3084, 2950, 2910, 1606, 1481, OCH₂_,_m_i_n_o_r), 4.48-4.47 (m, 2H, Cp-H_m_i_n_o_r), 4.47-4.42 (m, 6H, Cp-

3 2 2

1

4

444, 1407, 1378, 1353, 1321, 1293, 1265, 1228, 1184, 1143, H_m_a_j_o_r, OCH₂_,_m_a_j_o_r), 4.31-4.30 (m, 2H, Cp-H_m_i_n_o_r), 4.30-4.29 (m,

104, 1085, 1035, 998, 952, 921, 894, 814, 733, 679, 528, 490, 2H, Cp-H_m_a_j_o_r), 4.29 (s, 10H, Cp-H_m_i_n_o_r), 4.27-4.22 (m, 4H,

65, 429. HRMS (ESI) m/z: calculated for ([M]): 930.0176; NCH₂_,_m_i_n_o_r), 4.19 (s, 10H, Cp-H_m_a_j_o_r), 4.18-4.09 (m, 4H,

1

3

found: 930.0177.

NCH₂_,_m_a_j_o_r). C-NMR (175 MHz, CD Cl , 25 °C): δ = 178.9 (2C,

2 2

5

Synthesis of rac-bis[µ-[(η -2-(4',5'-Dihydro-4',4'-dimethyl-2'- C=N), 178.7 (2C, C=N), 84.1 (2C, Cp-C), 83.3 (2C, Cp-C), 82.4

oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

5

(2C, OCH ), 82.1 (2C, OCH ), 73.3 (2C, Cp-C), 73.2 (2C, Cp-C),

2 2

cyclopentadienyl) ferrocene]] digold(I) (Me FOMeAu(I)). 72.7 (2C, Cp-C), 72.1 (2C, Cp-C), 72.0 (2C, Cp-C), 71.9 (2C, Cp-

2

According to GP4 the methylated dimethyl-oxazoline C), 70.2 (10C, Cp-C), 70.1 (10C, Cp-C), 68.0 (2C, Cp-C), 67.9 (2C,

Me FOMe (100.0 mg, 0.336 mmol, 1.0 equiv) was dissolved in Cp-C), 57.0 (2C, NCH ), 56.9 (2C, NCH ). IR (in CH Cl ): 휈̃ = 1619,

2

Et O (3.4 mL) and treated with t-BuLi (207.8 µL, 22.6 mg, 1480, 1461, 1434, 1378, 1337, 1293, 1225, 1152, 1104, 1038,

2

0

.353 mmol, 1.1 equiv, 1.7M in pentane). After 30 min at 0 °C 998, 968, 951, 815, 730, 552, 508, 488, 460. HRMS (ESI) m/z:

chloro(dimethyl sulfide)gold(I) (79.3 mg, 0.269 mmol, calculated for ([M]): 901.9863; found: 901.9866.

.8 equiv) and toluene (1.7 mL) were added. Washing 3 times Synthesis of rac-bis[µ-[(η -2-(4',5'-Dihydro-4',4'-dimethyl-2'-

5

0

5

with pentane afforded the product as orange solid (105.5 mg, oxazolyl-κN)-cyclopentadienyl-κC)(η -

.107 mmol, 80%) based on chloro(dimethyl sulfide)gold(I). cyclopentadienyl)ferrocene]] digold(I) (Me FOAu(I)). The

0

2

The enantiomers (R ,R ), (S ,S ) and their diastereomer (S ,R ) dimethyl-oxazoline Me FO (105.6 mg, 0.373 mmol, 1.0 equiv)

p

2

were formed in a dr = 1:2.8, but the ratio cannot be assigned was dissolved in toluene (3.7 mL) and TMEDA (111.2 µL,

to the disastereomers. C H Au Fe N O : MW: 986.28 g/mol. 86.8 mg, 0.746 mmol, 2.0 equiv) and treated with n-BuLi

3

2

36

2

2 2 2

1

MP: >172 °C (decomp.). H-NMR (700 MHz, CD Cl , 25 °C): (279.7 µL, 28.7 mg, 0.448 mmol, 1.2 equiv, 1.6M in hexane) at

2

δ = 4.33-4.31 (m, 6H, Cp-H_m_a_j_o_r, Cp-H_m_i_n_o_r, OCH_m_i_n_o_r), 4.28 (d,

J = 8.1, 2H, OCH_m_a_j_o_r), 4.178 (d, J = 8.1, 2H, OCH_m_a_j_o_r), 4.176 (s, temperature and chloro(dimethyl sulfide)gold(I) (109.9 mg,

0H, Cp-H_m_i_n_o_r), 4.16 (d, J = 8.4, 2H, OCH_m_i_n_o_r), 4.11 (s, 10H, Cp- 0.373 mmol, 1.0 equiv) was added. The reaction mixture was

78 °C. After 2h the reaction mixture was warmed to room

1

2

0 | J. Name., 2012, 00, 1-3

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Page 21 of 25

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Journal Name

ARTICLE

stirred overnight, filtered over celite with CH Cl and washed 0.020 mmol,

pentane and acetone to yield the product as brown-orange 1201.54 g/mol. MP: >161 °C (decomp.). [α]

77%).

C H Au Cl Fe N O Si : MW:

View Article Online

2 2 2 2

2

38 52

2

20

DOI: 10.1039/C8DT00109J

:



46.5 (c = 0.06

D

1

solid (111.2 mg, 0.116 mmol, 62%). The enantiomers (R ,R ), mg/mL, CH Cl ). H-NMR (400 MHz, CD Cl , 25 °C): δ = 5.08 (d,

p

2

(

S ,S ) and their diastereomer (S ,R ) were formed in a J = 2.7, 2H, Cp-H), 5.01-4.95 (m, 2H, OCH CHN), 4.613 (d,

p

2

dr = 1:1.2, but the ratio cannot be assigned to the J = 2.7, 2H, Cp-H), 4.606 (s, 10H, Cp-H), 4.54-4.49 (m, 2H,

disastereomers. C H Au Fe N O : MW: 958.22 g/mol. MP: OCH CHN), 4.46 (dd, J = 5.7, 9.0, 2H, OCH CHN), 2.07-1.98 (m,

3

0

32

2

1

>

4

152 °C (decomp.). H-NMR (700 MHz, CD Cl , 25 °C): δ = 4.88- 2H, CH(CH ) ), 0.93 (d, J = 7.0, 6H, CH(CH ) ), 0.85 (d, J = 7.0,

2 2 3 2 3 2

.86 (m, 2H, Cp-H_m_a_j_o_r), 4.84-4.83 (m, 2H, Cp-H_m_i_n_o_r), 4.47-4.46 6H, CH(CH ) ) 0.35 (s, 18H, Si(CH ) ). C-NMR (125 MHz,

13

3 2

3 3

(

m, 2H, Cp-H_m_a_j_o_r), 4.46-4.45 (m, 2H, Cp-H_m_i_n_o_r), 4.34-4.32 (m, CD Cl , 25 °C): δ = 177.9 (2C, C=N), 88.9 (2C, Cp-C), 81.0 (2C,

2 2

4

H, Cp-H_m_a_j_o_r₊_m_i_n_o_r), 4.28 (d, J = 8.4, 2H, OCH₂_,_m_a_j_o_r), 4.27 (d, Cp-C), 78.6 (2C, Cp-C), 73.4 (2C, Cp-C), 73.0 (2C, Cp-C), 72.8

J = 8.2, 2H, OCH₂_,_m_i_n_o_r), 4.26 (s, 10H, Cp-H_m_a_j_o_r), 4.17 (s, 10H, Cp- (10C, Cp-C), 70.7 (2C, NCH), 68.4 (2C, OCH ), 30.9 (2C,

2

H_m_i_n_o_r), 4.15 (d, J = 8.4, 2H, OCH₂_,_m_a_j_o_r), 4.14 (d, J = 8.2, 2H, CH(CH ) ), 19.0 (2C, CH(CH ) ), 16.2 (2C, CH(CH ) ), 0.8 (2C,

3 2

OCH₂_,_m_i_n_o_r), 1.65 (s, 6H, NCCH₃_,_m_a_j_o_r), 1.61 (s, 6H, NCCH₃_,_m_i_n_o_r), Si(CH ) ). IR (in CDCl ): 휈̃ = 2955, 2903, 2186, 1617, 1481, 1434,

3 3

3

13

1

.59 (s, 6H, NCCH₃_,_m_i_n_o_r), 1.56(s, 6H, NCCH₃_,_m_a_j_o_r). C-NMR 1390, 1233, 1184, 1129, 1108, 1076, 1056, 1004, 953, 888,

(

8

175 MHz, CD Cl , 25 °C): δ = 176.7 (2C, C=N), 176.5 (2C, C=N), 836, 756, 733, 695, 626, 612, 493, 456. HRMS (ESI) m/z:

2



5.52 (2C, Cp-C), 85.47 (2C, Cp-C), 82.6 (2C, Cp-C), 82.4 (2C, Cp- calculated for ([M+Na ): 1223.0870; found: 1223.0863.

5

C), 79.2 (2C, OCH ), 79.1 (2C, OCH ), 73.4 (2C, Cp-C), 73.2 (2C, Synthesis of dichlorobis[µ-[(η -(S,R )-2-(4'-tert-butyl-4',5'-

2

p

5

Cp-C), 72.8 (2C, Cp-C), 72.4 (2C, Cp-C), 72.3 (2C, Cp-C), 72.0 dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

2C, Cp-C), 70.11 (10C, Cp-C), 70.05 (10C, Cp-C), 68.89 (2C, cyclopentadienyl) ferrocene]] digold(II) (tBuFOMeAu(II)Cl).

NC(CH ) ), 68.86 (2C, NC(CH ) ), 29.94 (2C, NC(CH ) ), 29.91 According to GP5 gold(I) complex tBuFOMeAu(I) (10.1 mg,

(

3

2

3 2

(

2C, NC(CH ) ), 29.0 (2C, NC(CH ) ), 28.9 (2C, NC(CH ) ). IR (in 0.010 mmol, 1.0 equiv) was dissolved in CHCl (1.0 mL) and

3 2 3 2 3 2 3

CH Cl ): 휈̃ = 2963, 2925, 2894, 1607, 1476, 1459, 1430, 1367, stirred at 50 °C for 24 h. After cooling to room temperature the

2

1

9

330, 1262, 1213, 1192, 1137, 1104, 1057, 1036, 998, 974, reaction mixture was filtered over celite with CH Cl . Washing

2 2

29, 811, 734, 702, 638, 546, 515, 495, 474, 438. HRMS (ESI) 3 times with pentane afforded the product as violet solid

+

m/z: calculated for ([M+H] ): 959.0567; found: 959.0570.

Synthesis of dichlorobis[µ-[(η -(S,Rp)-2-(4'-isopropyl-4',5'- 1113.28 g/mol. MP: >189 °C (decomp.). [α]

dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC1)(η -

(9.4 mg, 0.008 mmol, 87%). C H Au Cl Fe N O : MW:

36

44

2

20

2 2 2

5

: 67.9 (c = 0.09

D

5

1

mg/mL, CH Cl ). H-NMR (700 MHz, CDCl , 25 °C): δ = 4.95 (dd,

2 2 3

cyclopentadienyl) ferrocene]] digold(II) (iPrFOMeAu(II)Cl). J = 5.7, 9,1, 2H, OCH CHN), 4.88 (d, J = 2.6, 2H, Cp-H), 4.63 (d, J

2

According to GP5 gold(I) complex iPrFOMeAu(I) (130.2 mg, = 2.6, 2H, Cp-H), 4.59-4.56 (m, 4H, OCH CHN), 4.52 (s, 10H, Cp-

2

13

0

.128 mmol, 1.0 equiv) was dissolved in CHCl (6.4 mL) and H), 2.25 (s, 6H, CH ), 0.98 (s, 18H, C(CH ) ). C-NMR (175 MHz,

3 3 3 3

stirred at 50 °C for 24 h. Washing 3 times with pentane CD Cl , 25 °C): δ = 178.9 (2C, C=N), 86.3 (2C, Cp-C), 83.2 (2C,

2

afforded the product as violet solid (120.8 mg, 0.111 mmol, Cp-C), 78.4 (2C, Cp-C), 74.9 (2C, Cp-C), 73.7 (10C, Cp-C), 71.9

8

7%). C H Au Cl Fe N O : MW: 1085.23 g/mol. MP: >195 °C (NCH), 71.6 (OCH ), 67.3 (2C, Cp-C), 34.7 (2C, C(CH ) ), 26.4

3

4

40

2

3 3

2

0

1

(decomp.). [α]_D

:



21.7 (c = 0.17 mg/mL, CH Cl ). H-NMR (700 (6C, C(CH ) ), 15.8 (2C, CH ). IR (in CH Cl ): 휈̃ = 2957, 2923,

2

3 3

3

2

MHz, CDCl , 25 °C): δ = 5.04-5.00 (m, 2H, OCH CHN), 4.86 (d, J 2870, 1601, 1480, 1466, 1430, 1409, 1399, 1369, 1322, 1293,

3

2

=

2

2.6, 2H, Cp-H), 4.59-4.55 (m, 2H, OCH CHN), 4.58 (d, J = 2.6, 1264, 1213, 1147, 1098, 1040, 1000, 959, 924, 891, 735, 702,

2



H, Cp-H), 4.51 (s, 10H, Cp-H), 4.42 (dd, J = 5.8, 8.8, 2H, 682, 517, 480, 460. HRMS (ESI) m/z: calculated for ([M



Cl] ):

OCH CHN), 2.19 (s, 6H, CH ), 2.07-2.01 (m, 2H, CH(CH ) ), 0.91 1077.1118; found: 1077.1112.

2

3

3 2

13

5

(

d, J = 6.9, 6H, CH(CH ) ), 0.83 (d, J = 6.9, 6H, CH(CH ) ). C- Synthesis of dichlorobis[µ-[(η -(S,S )-2-(4',5'-5'H-Indeno[1,2-

3 2 3 2 p

NMR (175 MHz, CDCl , 25 °C): δ = 178.2 (2C, C=N), 85.1 (2C, d]-4',5'-dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-

3

5

Cp-C), 85.0 (2C, Cp-C), 77.3 (2C, Cp-C), 74.4 (2C, Cp-C), 73.4 κC)(η -cyclopentadienyl)

ferrocene]]

digold(II)

(10H, Cp-C), 70.7 (2C, NCH), 67.6 (2C, Cp-C), 67.5 (2C, OCH₂), (IndFOMeAu(II)Cl).

According to

GP5

gold(I)

3

0.6 (2C, CH(CH ) ), 18.8 (2C, CH(CH ) ), 16.2 (2C, CH ), 15.5 complex IndFOMeAu(I) (15.1 mg, 0.014 mmol, 1.0 equiv) was

3 2 3 2 3

(

2C, CH(CH ) ). IR (in CH Cl ): 휈̃ = 2960, 1614, 1467, 1437, 1409, dissolved in CHCl (1.4 mL) and stirred at 50 °C for 4 days. After

3

2

3

1

8

391, 1328, 1287, 1263, 1212, 1099, 1056, 1001, 954, 888, cooling to room temperature the reaction mixture was filtered

30, 736, 702, 516, 494, 476. HRMS (ESI) m/z: calculated for over celite with CH Cl . Washing 3 times with pentane

2



([M



Cl] ): 1049.0805; found: 1049.0813.

afforded the product as violet solid (12.1 mg, 0.010 mmol,

5

Synthesis of dichlorobis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'- 75%). C H Au Cl Fe N O : MW: 1177.29 g/mol. MP: >186 °C

dihydro-2'-oxazolyl-κN)-3-trimethylsilyl-cyclopentadienyl-

κC)(η -cyclopentadienyl)

p

42 36

2

2 2 2

0

1

(decomp.). [α]_D: 15.6 (c = 0.17 mg/mL, CH Cl ). H-NMR (700

digold(II) MHz, CD Cl , 25 °C): δ = 7.20 (d, J = 7.7, 2H, Ar-H), 7.17-7.13

2 2

2

5

ferrocene]]

According to

(iPrFOTMSAu(II)Cl).

GP5

gold(I) (m, 4H, Ar-H), 6.51-6.48 (m, 2H, Ar-H), 6.41 (d, J = 8.2, 2H,

complex iPrFOTMSAu(I) (30.0 mg, 0.027 mmol, 1.0 equiv) was NCH), 5.72-5.70 (m, 2H, OCH), 4.80 (d, J = 2.4, 2H, Cp-H), 4.61

dissolved in CHCl (2.7 mL) and stirred at 50 °C for 6 days. After (d, J = 2.4, 2H, Cp-H), 4.54 (s, 10H, Cp-H), 3.51 (dd, J = 7.5, 17.9,

3

13

cooling to room temperature the reaction mixture was filtered 2H, CH ), 3.36 (d, J = 17.9, 2H, CH ), 2.30 (s, 6H, CH ). C-NMR

2

3

over celite with CH Cl . Washing 2 times with pentane, (175 MHz, CD Cl , 25 °C): δ = 178.2 (2C, C=N), 139.3 (2C, Ar-C),

2

followed by a flash column chromatography over silica gel with 139.0 (2C, Ar-C), 129.7 (2C, Ar-C), 128.5 (2C, Ar-C), 125.5 (2C,

CH Cl /PE = 3:2 afforded the product as violet solid (24.5 mg, Ar-C), 125.0 (2C, Ar-C), 86.5 (2C, OCH), 85.4 (2C, Cp-C), 84.4

2

J. Name., 2013, 00, 1-3 | 21

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Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Page 22 of 25

ARTICLE

Journal Name

(

7

2C, Cp-C), 77.5 (2C, NCH), 74.3 (2C, Cp-C), 73.7 (10C, Cp-C), (2C, CH(CH ) ). IR (in CH Cl ): 휈̃ = 2956, 2921, 1725, 1610, 1465,

2.6 (2C, Cp-C), 68.5 (2C, Cp-C), 39.8 (2C, CH ), 15.5 (2C, CH ). 1435, 1408, 1390, 1286, 1262, 1211, 1146, 1098, 1055, 1033,

2 3

3 2 2 2

View Article Online

DOI: 10.1039/C8DT00109J

IR (in CH Cl ): 휈̃ = 2954, 2923, 1600, 1462, 1430, 1382, 1316, 1000, 954, 924, 887, 830, 736, 703, 680, 561, 516, 494, 475,

2



1

8

292, 1253, 1207, 1171, 1144, 1105, 1089, 1052, 1016, 927, 457. HRMS (ESI) m/z: calculated for ([M

98, 822, 752, 735, 709, 517, 505, 490, 467. HRMS (ESI) m/z: found: 1093.0299.

calculated for ([M

Synthesis of dichlorobis[µ-[(η -(S,S )-2-(4',5'-diphenyl-4',5'- dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC1)(η -

dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC)(η -

Br] : 1093.0302;



5



Na] ): 1199.0079; found: 1199.0089.

Synthesis

of

diiodobis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'-

p

5

p

5

cyclopentadienyl) ferrocene]] digold(II) (iPrFOMeAu(II)I).

cyclopentadienyl) ferrocene]] digold(II) (Ph FOMeAu(II)Cl). Method A: The gold(I) complex iPrFOMeAu(I) (20.4 mg,

2

According to GP5 gold(I) complex Ph FOMeAu(I) (16.4 mg, 0.020 mmol, 1.0 equiv) was dissolved in toluene (2.0 mL) and

2

0

.013 mmol, 1.0 equiv) was dissolved in CHCl (1.3 mL) and benzyliodide (10.1 µL, 17.5 mg, 0.080 mmol, 4.0 equiv) was

3

stirred at 50 °C for 6 days. After cooling to room temperature added. After stirring at room temperature for 2 h the reaction

the reaction mixture was filtered over celite with CH Cl . mixture was filtered over celite with CH Cl . Washing 3 times

2

Washing 3 times with pentane afforded the product as violet with pentane afforded the product as green solid (12.8 mg,

solid (11.7 mg, 0.009 mmol, 69%). C H Au Cl Fe N O : MW: 0.010 mmol, 50%). Method B: The gold(I) complex

52

44

2

20

1

305.46 g/mol. MP: 197 °C. [α] : 185.9 (c = 0.003 mg/mL, iPrFOMeAu(I) (38.1 mg, 0.038 mmol, 1.0 equiv) was dissolved

D

1

CH Cl ). H-NMR (700 MHz, CD Cl , 25 °C): δ = 7.54-7.47 (m, in toluene (3.8 mL) and iodomethane (3.5 µL, 8.0 mg,

2

1

6

0H, Ph-H), 7.41-7.35 (m, 6H, Ph-H), 7.22-7.21 (m, 4H, Ph-H), 0.056 mmol, 1.5 equiv) was added. After stirring at 50 °C for

.01 (d, J = 8.8, 2H, OCHPh), 5.48 (d, J = 8.8, 2H, NCHPh). 4.90 3 h the reaction mixture was cooled to room temperature and

(

d, J = 2.6, 2H, Cp-H), 4.63 (d, J = 2.6, 2H, Cp-H), 4.58 (s, 10H, the solvent was removed under reduced pressure. Washing 3

13

Cp-H), 2.22 (s, 6H, CH₃). C-NMR (175 MHz, CD Cl , 25 °C): δ = times with pentane afforded the product as green solid

2

1

79.0 (2C, C=N), 139.0 (2C, Ar-C), 137.8 (2C, Ar-C), 129.8 (2C, (22.1 mg, 0.017 mmol, 46%). Method C: The gold(I) complex

Ar-C), 129.58 (4C, Ar-C), 129.56 (2C, Ar-C), 128.8 (4C, Ar-C), iPrFOMeAu(I) (20.3 mg, 0.020 mmol, 1.0 equiv) was dissolved

27.8 (4C, Ar-C), 126.7 (4C, Ar-C), 91.6 (2C, OCH), 85.8 (2C, Cp- in CH Cl (2.0 mL) and iodine (5.1 mg, 0.020 mmol, 1.0 equiv)

1

2

C), 84.8 (2C, Cp-C), 78.1 (2C, NCH), 74.7 (2C, Cp-C), 74.4 (2C, was added. After stirring at room temperature for 2 h the

Cp-C), 73.7 (10C, Cp-C), 67.4 (2C, Cp-C), 15.7 (2C, CH ). IR (in reaction mixture was filtered over celite with CH Cl . Washing

3

2

CH Cl ): 휈̃ = 2925, 1601, 1495, 1429, 1375, 1280, 1196, 1146, 3 times with pentane afforded the product as green solid

2

1

100, 1030, 1002, 966, 926, 822, 758, 697, 604, 505, 486, 461. (10.1 mg, 0.008 mmol, 40%). C H Au I Fe N O : MW:

34 40 2 2 2 2 2



20

HRMS (ESI) m/z: calculated for ([M

found: 1269.1104.

Synthesis of dibromobis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'- 5.23 (m, 2H, OCH CHN), 5.04 (d, J = 2.5, 2H, Cp-H), 4.59 (s, 10H,

dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC1)(η -



Cl] ): 1269.1119; 1268.14 g/mol. MP: >150°C (decomp.). [α] : 57.1 (c = 0.11

D

1

mg/mL, CH Cl ). H-NMR (400 MHz, CD Cl , 25 °C): δ = 5.29-

2

5

p

2

5

Cp-H), 4.56 (d, J = 2.5, 2H, Cp-H), 4.51-4.46 (m, 4H, OCH CHN),

2

cyclopentadienyl) ferrocene]] digold(II) (iPrFOMeAu(II)Br). 2.22 (s, 6H, CH ), 2.02-1.92 (m, 2H, CH(CH ) ), 0.90 (d, J = 7.0,

3

3 2

13

Method A: The gold(I) complex iPrFOMeAu(I) (7.2 mg, 6H, CH(CH ) ), 0.79 (d, J = 7.0, 6H, CH(CH ) ). C-NMR (175

3

2

3 2

0

.007 mmol, 1.0 equiv) was dissolved in toluene (0.7 mL) and MHz, CDCl , 25 °C): δ = 178.8 (2C, C=N), 84.8 (2C, Cp-C), 83.2

3

benzylbromide (3.4 µL, 4.9 mg, 0.028 mmol, 4.0 equiv) was (2C, Cp-C), 82.0 (2C, Cp-C), 74.6 (2C, Cp-C), 73.5 (10C, Cp-C),

added. After stirring at 50 °C for 24 h the reaction mixture was 72.5 (2C, Cp-C), 71.6 (2C, NCH), 70.6 (2C, OCH ), 30.3 (2C,

2

cooled to room temperature and filtered over celite with CH(CH ) ), 18.8 (2C, CH(CH ) ), 15.5 (2C, CH ), 15.4 (2C,

3

2

3 2

3

CH Cl . Washing 3 times with pentane afforded the product as CH(CH ) ). IR (in CH Cl ): 휈̃ = 2957, 2924, 2871, 1614, 1584,

2

3 2

2

blue solid (4.2 mg, 0.004 mmol, 50%). Method B: The gold(I) 1507, 1484, 1433, 1408, 1391, 1316, 1286, 1261, 1210, 1148,

complex iPrFOMeAu(I) (10.0 mg, 0.010 mmol, 1.0 equiv) and 1105, 1095, 1053, 1034, 999, 958, 939, 887, 826, 737, 514,



1

6

,2-dibromotetrachloroethane

.0 equiv) were dissolved in CH Cl (1.0 mL). After stirring at found: 1141.0170.

(19.3 mg,

0.059 mmol, 477. HRMS (ESI) m/z: calculated for ([MI] ): 1141.0160;

2

room temperature for 30 min the reaction mixture was filtered The byproducts iPrFOMe₂(5.6 mg, 0.017 mmol, 23%) and

over celite with CH Cl . Washing 3 times with pentane iPrFOMe)₂(4.1 mg, 0.007 mmol, 17%) could be isolated from

(

2

afforded the product as blue solid (11.3 mg, 0.010 mmol, 98%). the pentane phase by column chromatography (silica gel,

C H Au Br Fe N O : MW: 1174.14 g/mol. MP: >196 °C PE/EE = 10:1 to 2:1). (iPrFOMe)₂was obtained as yellow oil.

3

4

40

2

2 2

0

1

(

decomp.). [α]_D

:



42.2 (c = 0.13 mg/mL, CH Cl ). H-NMR (400 (S,R ,S,R )-2,2'-bis[(4-isopropyl-4,5-dihydro-2-oxazolyl)-3-

2

p

MHz, CD Cl , 25 °C): δ = 5.14-5.08 (m, 2H, OCH CHN), 4.89 (d, J methyl] 1,1'-biferrocenyl ((iPrFOMe) ). C H Fe N O : MW:

2

34 40

2 2 2

20

1

=

2.4, 2H, Cp-H), 4.59 (d, J = 2.4, 2H, Cp-H), 4.57-4.52 (m, 2H, 620.40 g/mol. [α]_D

: 111.4 (c = 1.00 mg/mL, CH Cl ). H-NMR

2 2

OCH CHN), 4.54 (s, 10H, Cp-H), 4.46 (dd, J = 5.8, 9.0, 2H, (700 MHz, CD Cl , 25 °C): δ = 4.61 (d, J = 2.4, 2H, Cp-H),4.30 (d,

2

OCH CHN), 2.22 (s, 6H, CH ), 2.05-1.96 (m, 2H, CH(CH ) ), 0.92 J = 2.4, 2H, Cp-H), 3.99 (s, 10H, Cp-H), 3.97-3.95 (m, 4H,

2

3

3 2

13

(

d, J = 7.0, 6H, CH(CH ) ), 0.83 (d, J = 7.0, 6H, CH(CH ) ). C- OCH CHN), 3.88-3.85 (m, 2H, OCH CHN), 2.21 (s, 6H, CH ),

3 2 3 2 2 2 3

NMR (100 MHz, CD Cl , 25 °C): δ = 178.5 (2C, C=N), 85.2 (2C, 1.81-1.75 (m, 2H, CH(CH ) ), 0.97 (d, J = 6.9, 6H, CH(CH ) ),

2

3 2

1

3

Cp-C), 84.3 (2C, Cp-C), 79.5 (2C, Cp-C), 74.5 (2C, Cp-C), 73.6 0.95 (d, J = 6.9, 6H, CH(CH ) ). C-NMR (100 MHz, CD Cl ,

3

2

(

10C, Cp-C), 71.0 (2C, NCH), 69.2 (2C, OCH ), 68.4 (2C, Cp-C), 25 °C): δ = 165.1 (2C, C=N), 86.4 (2C, Cp-C), 84.6 (2C, Cp-C),

2

3

0.8 (2C, CH(CH ) ), 18.9 (2C, CH(CH ) ), 16.0 (2C, CH ), 15.5 72.4 (2C, NCH), 72.3 (2C, Cp-C), 71.9 (12C, Cp-C), 70.4 (2C, Cp-

3

2

3 2

3

2

2 | J. Name., 2012, 00, 1-3

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Page 23 of 25

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Journal Name

C), 69.0 (2C, OCH ), 33.0 (2C, CH(CH ) ), 18.5 (2C, CH(CH ) ),

ARTICLE

2

3 2

View Article Online

DOI: 10.1039/C8DT00109J

1

2

1

8.3 (2C, CH(CH ) ), 15.4 (2C, CH ). IR (in CH Cl ): 휈̃ = 2957,

3 2 3 2 2

925, 2902, 2875, 1648, 1480, 1466, 1425, 1378, 1203, 1106,

053, 1023, 970, 818, 511, 480. HRMS (ESI) m/z: calculated for

+

([M+H] ): 621.1862; found: 621.1830.

5

Synthesis of diacetatobis[µ-[(η -(S,R )-2-(4'-isopropyl-4',5'-

p

5

dihydro-2'-oxazolyl-κN)-3-methyl-cyclopentadienyl-κC1)(η -

cyclopentadienyl) ferrocene]] digold(II) (iPrFOMeAu(II)OAc).

The gold(II) complex iPrFOMeAu(II)Cl (20.3 mg, 0.019 mmol,

1

.0 equiv) and silver acetate (6.2 mg, 0.037 mmol, 2.0 equiv)

were dissolved in CH Cl (1.2 mL). After stirring at room

2

temperature overnight in the dark the reaction mixture was

filtered over celite with CH Cl and the solvent was removed

2

under reduced pressure. Washing 3 times with pentane

afforded the product as red solid (20.6 mg, 0.018 mmol, 96%).

C H Au Fe N O : MW: 1132.42 g/mol. MP: >166°C

1

2

a) C. J. Richards, in Chiral Ferrocenes in Asymmetric Catalysis

(

Eds: L.-X. Dai, X.-L. Hou,), Wiley-VCH, Weinheim, 2010, pp.

38

46

2

2 2 6

3

37-368; b) R. Peters, D. F. Fischer and S. Jautze, Top.

2

0

1

(

^d^e^c^o^m^p^.⁾^.^[^α^]D : 423.5 (c = 0.12 mg/mL, CH Cl ). H-NMR (700

2 2

Organomet. Chem., 2011, 33, 139.

MHz, CDCl , 25 °C): δ = 4.62 (d, J = 2.1, 2H, Cp-H), 4.54 (s, 10H,

For monopalladacycles based on ferrocene or cobalt

sandwich complexes, see e.g.: a) Y. Donde and L. E.

Overman, J. Am. Chem. Soc. 1999, 121, 2933; b) L. E.

Overman, C. E. Owen, M. M. Pavan and C. J. Richards, Org.

3

Cp-H), 4.53-4.49 (m, 2H, OCH CHN), 4.47 (d, J = 2.1, 2H, Cp-H),

2

4

.36 (dd, J = 5.8, 8.6, 2H, OCH CHN), 4.32-4.28 (m, 2H,

2

OCH CHN), 2.20-2.15 (m, 2H, CH(CH ) ), 2.16 (s, 6H, OCOCH ),

2

3 2

3

Lett., 2003, 5, 1809; c) C. E. Anderson, Y. Donde, C. J. Douglas

2

6

.02 (s, 6H, CH ), 0.85 (d, J = 7.1, 6H, CH(CH ) ), 0.81 (d, J = 7.1,

3

1

3 2

and L. E. Overman, J. Org. Chem., 2005, 70, 648; d) M. E.

Weiss, D. F. Fischer, Z.-q. Xin, S. Jautze, W. B. Schweizer and

R. Peters, Angew. Chem. Int. Ed., 2006, 45, 5694; e) H.

Nomura and C. J. Richards, Chem. Eur. J., 2007, 13, 10216; f)

Z.-q. Xin, D. F. Fischer and R. Peters, Synlett, 2008, 1495; g) R.

3

H, CH(CH ) ). C-NMR (175 MHz, CDCl , 25 °C): δ = 178.7 (2C,

3

2

3

C=N), 175.6 (2C, OCOCH ), 85.3 (2C, Cp-C), 85.1 (2C, Cp-C), 74.2

3

(

2C, Cp-C), 73.7 (2C, Cp-C), 73.2 (10C, Cp-C), 70.0 (OCH ), 67.9

2

NCH), 67.2 (2C, Cp-C), 30.5 (2C, CH(CH ) ), 24.2 (2C, CH ), 18.8

3

2

3

Peters, Z.-q. Xin and F. Maier, Chem. Asian J., 2010, 5, 1770;

2C, CH(CH ) ), 15.7 (2C, CH ), 15.5 (2C, CH(CH ) ). IR (in CDCl ):

3

2

3

3 2

3

h) M. Weber and R. Peters, J. Org. Chem., 2012, 77, 10846; i)

S. H. Eitel, S. Jautze, W. Frey and R. Peters, Chem. Sci., 2013,

휈̃ = 2960, 2924, 1613, 1483, 1434, 1410, 1361, 1299, 1259,

214, 1096, 1000, 955, 921, 823, 729, 665, 516, 479. HRMS

1

4, 2218; j) J. M. Bauer, W. Frey and R. Peters, Angew. Chem.





Int. Ed., 2014, 53, 7634; k) T. Hellmuth, W. Frey and R.

Peters, Angew. Chem. Int. Ed., 2015, 54, 2788; l) C. Schrapel

and R. Peters, Angew. Chem. Int. Ed., 2015, 54, 10289.

(ESI) m/z: calculated for ([MCOCH ] ): 1089.1198;

3

found: 1089.1005.

3

For bispalladacycles, see e.g.: a) S. Jautze and R. Peters,

Angew. Chem. Int. Ed., 2008, 47, 9284; b) S. Jautze, S.

Conflicts of interest

There are no conflicts to declare.

Diethelm, W. Frey and R. Peters, Organometallics, 2009, 28

,

2

001; c) M. Weber, S. Jautze, W. Frey and R. Peters, J. Am.

Chem. Soc., 2010, 132, 12222; d) M. Weber, W. Frey and R.

Peters, Adv. Synth. Catal., 2012, 354, 1443; e) M. Weber, W.

Frey and R. Peters, Angew. Chem. Int. Ed., 2013, 52, 13223; f)

T. Hellmuth, S. Rieckhoff, M. Weiss, K. Dorst, W. Frey and R.

Acknowledgements

Peters, ACS Catal., 2014,

ACS Catal., 2015, , 310.

a) H. Huang and R. Peters, Angew. Chem. Int. Ed., 2009, 48

604; b) M. Weiss, W. Frey and R. Peters, Organometallics,

4, 1850; g) M. Weiss and R. Peters,

We thank the Deutsche Forschungsgemeinschaft (PE 818/6-1)

for their financial support allowing to conduct this project. R.P.

and M.A.G. also thank Hoffmann-La Roche for their financial

support. The authors thank M.Sc. Heiko Bamberger (research

group of Prof. J. van Slageren, Universität Stuttgart) for

recording CD spectra.

5

4

5

,

2

012, 31, 6365.

Selected reviews: a) A. S. K. Hashmi and F. D. Toste (eds.),

Modern Gold Catalyzed Synthesis, Wiley-VCH, Weinheim,

2

012; b) A. S. K. Hashmi, Acc. Chem. Res., 2014, 47, 864; c)

Y.-M. Wang, A. D. Lackner and F. D. Toste, Acc. Chem.

Res., 2014, 47, 889; d) C. Obradors and A. M. Echavarren,

Acc. Chem. Res., 2014, 47, 902; e) C. Obradors and A. M.

Notes and references

Echavarren, Chem. Commun., 2014, 50

,

16; f) H.

§

The compound codes used in this manuscript were created in

Raubenheimer and H. Schmidbaur, J. Chem. Educ., 2014, 91

,

the following way:

2

024; g) I. Braun, A. M. Asiri and A. S. K. Hashmi, ACS

Catal., 2013,

3

, 1902; h) N. Krause in Organometallics in

Synthesis: Fourth Manual (Ed. Lipshutz, B. H.), 2013, pp. 429-

5

40; i) M. Chiarucci and M. Bandini, Beilstein J. Org.

Chem., 2013, , 2586; j) A. Gomez-Suarez and S. P. Nolan,

9

Angew. Chem. Int. Ed., 2012, 51, 8156; k) A. Fürstner and P.

W. Davies, Angew. Chem. Int. Ed., 2007, 46, 3410; l) A. S. K.

Hashmi, Chem. Rev., 2007, 107, 3180; m) A. Arcadi, Chem.

Rev., 2008, 108, 3266; n) D. Gorin, B. Sherry and F. D. Toste,

Chem. Rev., 2008, 108, 3351.

J. Name., 2013, 00, 1-3 | 23

Please do not adjust margins

Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins

Page 24 of 25

ARTICLE

Journal Name

6

A planar chiral ruthenocenyl Au(I)PPh₃complex has been

reported by Herberich, but pure material could not be

solvents like 1,2-dichloroethane, see ref. 10 _V a _i _e _w a _A n _r _t d _i _c _l _e c _O i _n t _l e _i _n d _e

references.

DOI: 10.1039/C8DT00109J

obtained: G. E. Herberich, U. Englert and T. Wirth, Eur. J. 23 L.-X. Dai and X.-L. Hou, (eds.), Chiral Ferrocenes in

Inorg. Chem., 2005, 4924.

a) A. N. Nesmeyanov, E. G. Perevalova, D. A. Lemenovskii, A.

N. Kosina and K. I. Grandberg, Izv. Akad. Nauk. SSSR, Ser. 24 a) S. A. Herbert, D. C. Castell, J. Clayden and G. E. Arnott,

Khim., 1969, 2030; b) A. N. Nesmeyanov, E. G. Perevalova, K.

I. Grandberg, D. A. Lemenovskii, T. V. Baukova and O. B.

Afanassova, J. Organomet. Chem., 1974, 65, 131; c) K. I. 25 Our group applied Arnott’s method to diastereodivergent

Asymmetric Catalysis, Wiley-VCH, Weinheim, Germany,

2010.

7

Org. Lett., 2013, 15, 3334; b) for a related protocol, see: T.

Sammakia and H. A. Latham, J. Org. Chem., 1995, 60, 6002.

Grandberg and V. P. Dyadchenko, J. Organomet. Chem.,

994, 474, 1; d) K. Jacob, F. Voigt, K. Merzweiler and C.

Pietzsch, J. Organomet. Chem., 1997, 545-546, 421; e) K.

ortho-lithiations of chiral 1,2,3,4,5-pentaphenylferrocenes:

M. Ayerbe Garcia, W. Frey and R. Peters, Organometallics,

2014, 33, 1068.

1

Jacob, F. Voigt, K. Merzweiler, C. Wagner, P. Zanello, M. 26 C. J. Richards and A. W. Mulvaney, Tetrahedron: Asymmetry,

Fontani and C. Pietzsch, J. Organomet. Chem., 1998, 552 1996, , 1419.

65; f) F. Voigt, A. Fischer, C. Pietzsch and K. Jacob, Z. Anorg. 27 a) A. S. K. Hashmi, C. Lothschütz, R. Döpp, M. Ackermann, J.

,

7

2

Allg. Chem., 2001, 627, 2337; for a recent contribution see:

g) N. Meyer, H. Schucht, C. W. Lehmann, B. Weibert, R. F.

Winter, F. Mohr, Eur. J. Inorg. Chem. 2017, 521.

M. Ayerbe Garcia, W. Frey, M. Ringenberg, M. Schwilk and R.

Peters, Chem. Commun., 2015, 51, 16806.

De Buck Becker, M. Rudolph, C. Scholz and F. Rominger, Adv.

Synth. Catal., 2012, 354, 133; b) M. Livendahl, C. Goehry, F.

Maseras and A. M. Echavarren, Chem. Commun., 2014, 50

,

8

9

1533.

28 a) G. Zhang, L. Cui, Y. Wang and L. Zhang, J. Am. Chem. Soc.,

2010, 132, 1474; b) A. D. Melhado, W. E. Brenzovich, A. D.

Lackner and F. D. Toste, J. Am. Chem. Soc., 2010, 132, 8885;

For early, pioneering studies, see e.g.: a) H. Schmidbaur and

R. Franke, Inorg. Chim. Acta, 1975, 13, 85; b) H. Schmidbaur,

Acc. Chem. Res., 1975,

8

, 62; c) H. Schmidbaur, Angew.

c) T. de Haro and C. Nevado, J. Am. Chem. Soc., 2010, 132,

Chem. Int. Ed. Engl., 1976, 15, 728; d) H. Schmidbaur, J. R.

Mandl, F. E. Wagner, D. F. Van de Vondel and G. P. Van der

Kelen, J. Chem. Soc., Chem. Commun., 1976, 170; e) H.

Schmidbaur, J. R. Mandi, A. Frank and G. Huttner, Chem.

Ber., 1976, 109, 466; f) H. Schmidbaur, F. E. Wagner and A.

Wohlleben-Hammer, Chem. Ber., 1979, 112, 496.

0 For later studies, see for e.g.: a) A. A. Mohamed, H. E. Abdou

and J. P. Fackler Jr., Coord. Chem. Rev., 2010, 354, 1253; b) D.

Zopes, C. Hegemann, W. Tyrra and S. Mathur, Chem.

Commun., 2012, 48, 8805; c) D. Y. Melgarejo, G. M. Chiarella,

1512; d) G. Zhang, Y. Luo, Y. Wang and L. Zhang, Angew.

Chem. Int. Ed., 2011, 50, 4450; e) M. D. Levin and F. D. Toste,

Angew. Chem. Int. Ed., 2014, 53, 6211; f) W. J. Wolf, M. S.

Winston and F. D. Toste, Nat. Chem., 2014,

6, 159; g) M.

Joost, A. Zeineddine, L. Estevez, S. Mallet-Ladeira, K. Miqueu,

A. Amgoune and D. Bourissou, J. Am. Chem. Soc., 2014, 136

,

1

14654; h) C.-Y. Wu, T. Horibe, C. B. Jacobsen and F. D. Toste,

Nature, 2015, 517, 449; i) M. Joost, L. Estevez, K. Miqueu, A.

Amgoune and D. Bourissou, Angew. Chem. Int. Ed., 2015, 54

,

5236.

J. P. Fackler, Jr., L. M. Perez, A. Rodrigue-Witchel and C. 29 For similar observations, see e.g.: a) M. A. Bennett, S. K.

Reber, Inorg. Chem., 2011, 50, 4238.

Bhargava, K. D. Griffiths and G. B. Robertson, Angew. Chem.

Int. Ed. Engl., 1987, 26, 260; b) M. A. Bennett, D. C. R.

Hockless, A. D. Rae, L. L. Welling and A. C. Willis,

Organometallics, 2001, 20, 79.

II

1

1 For formation of Au compounds by comproportionation,

see e.g.: J. Coetzee, W. F. Gabrielli, K. Coetzee, O. Schuster,

S. D. Nogai, S. Cronje and H. G. Raubenheimer, Angew.

Chem. Int. Ed., 2007, 46, 2497.

30 Q. Glenadel, M. Bordy, S. Alazet, A. Tlili and T. Billard, Asian J.

2 a) T. Sammakia, H. A. Latham and D. R. Schaad, J. Org. Chem.,

Org. Chem., 2016, 5, 428

1

995, 60, 10; b) C. J. Richards, T. Damalidis, D. E. Hibbs and 31 Similar observation: M. A. Bennett, S. K. Bhargava, D. C. R.

M. B. Hursthouse, Synlett, 1995, 74; c) Y. Nishibayashi and S.

Uemura, Synlett, 1995, 79.

Hockless, L. L. Welling and A. C. Willis, J. Am. Chem. Soc.,

1996, 118, 10469.

32 C. Nottingham, R. Benson, H. Müller-Bunz and P. J. Guiry, J.

Org. Chem., 2015, 80, 10163.

33 T. N. Hooper, C. P. Butts, M. Green, M. F. Haddow, J. E.

McGrady and C. A. Russel, Chem. Eur. J., 2009, 15, 12196.

34 P. Braunstein, H. Lehner, D. Matt, K. Burgess and M. J.

Ohlmeyer, Inorg. Synth., John Wiley & Sons 2007, 218.

1

3 H. Schmidbaur, Chem. Soc. Rev., 1995, 24, 391.

4 H. Schmidbaur, Nature, 2001, 413, 31.

5 P. Pyykkö, Angew. Chem. Int. Ed., 2004, 43, 4412.

6 Y.-A. Lee and R. Eisenberg, J. Am. Chem. Soc., 2003, 125

778.

7 For Au(II) compounds formed by other metal oxidants, see

,

7

1

e.g.: a) H. H. Murray, A. M. Mazany and J. P. Fackler, Jr., 35 V. H. G. Rohde, P. Pommerening, H. F. T. Klare and M.

Organometallics, 1985, , 154; b) V.W.-W. Yam, S. W.-K. Choi Oestreich, Organometallics, 2014, 33, 3618.

and K.-K. Cheung, J. Chem. Soc. Chem. Commun, 1996, 1173; 36 D. F. Fischer, A. Barakat, Z.-q. Xin, M. E. Weiss and R. Peters,

c) V.W.-W. Yam, C.-K. Li, C.-L. Chan and K.-K. Cheung, Inorg. Chem. Eur. J., 2009, 15, 8722.

Chem., 2001, 40, 7054; d) M. D. Irwin, H. E. Abdou, A. A. 37 C. Bolm, K. Muñiz-Fernández, A. Seger, G. Raabe and K.

4

Mohamed and J. P. Fackler, Jr., Chem. Commun., 2003, 2882;

e) ref. 10c.

8 H. E. Abdou, A. A. Mohamed and J. P. Fackler Jr., Inorg.

Chem., 2007, 46, 9692.

9 N. Mirzadeh, M. A. Bennett and S. K. Bhargava, Coord. Chem.

Rev., 2013, 257, 2250.

Günther, J. Org. Chem., 1998, 63, 7860.

38 R. A. Arthurs, P. N. Horton, S. J. Coles and C. J. Richards,

Chem. Commun., 2016, 52, 7024.

39 D. Schmiel and H. Butenschön, Eur. J. Org. Chem., 2017,

3041.

1

2

40 J. García, A. Moyano and M. Rosol, Tetrahedron, 2007, 63

,

0 M. A. Bennett, S. K. Bhargava, D. C. R. Hockless, F. Mohr, K.

Watts, L. L. Welling and A. C. Willis, Z. Naturforsch. Teil B,

1907.

2

004, 59, 1563.

1 D. W. Slocum, S. P. Tucker and T. R. Engelmann, Tetrahedron

Lett., 1970, , 621.

2

9

2 It has been reported that bis-Au(II) complexes can be formed

from bis-Au(I) precursors by oxidation with chlorinated

2

4 | J. Name., 2012, 00, 1-3

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