Preparation, characterization and properties of dipolar 1,2-N,N-dimethylaminomethylferrocenylsilanes

Article abstract of DOI:10.1016/S0022-328X(02)01427-4

A series of substituted 1,2-N,N-dimethylaminomethlyferrocenyl compounds were synthesized and characterized by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR, ES-MS, IR, UV - vis and ⁵⁷Fe-M?ssbauer spectroscopy. The new (R,S)-2-(N,N-dimethylaminomethyl)ferrocenyl-(arly)silanes (R,S)-FcNSiMe_n(C₆H₄X)_m (n = 2-0, m = 1, X = p-F (5); m = 2, X = p-F (6); m = 3, X = p-F (7) and m = 1, X = p-Br (14) were formed by the reaction of 2-dimethylaminomethylferrocenyllithium FcNLi (1) with chloroarylsilanes ClSi(Me)_n (C₆H₄X)_m (n = 2-0, m = 1, X = p-F (2); m = 2, X = p-F (3); m = 3, X = p-F (4) and m = 1, X = p-Br (13)). The treatment of 5, 6 and 14 with gaseous hydrogen chloride or picric acid resulted in the formation of the hydrochloride complexes 9, 10, 15 and the picrates 11, 12 and 16. The treatment of 14 with LiR or Mg and DMF resulted in the formation of (R,S)-2-(N,N-dimethylaminomethyl)ferrocenyl(4-formylphenyl)dimethylsilane (18). The crystal structures of 7, 12 and 15 were determined by single crystal X-ray analyses. ⁵⁷Fe-M?ssbauer spectroscopy gives evidence of a significant electronic coupling between the ferrocenyl unit and the organic acceptor moiety of the molecules in the ground state.

Full text of DOI:10.1016/S0022-328X(02)01427-4

Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
www.elsevier.com/locate/jorganchem
Preparation, characterization and properties of dipolar 1,2-N,N-
dimethylaminomethylferrocenylsilanes
Christian Beyer a, Uwe Bohme a,*, Claus Pietzsch b, Gerhard Roewer a
¨
a Institut fur Anorganische Chemie, Technische Universitat Bergakademie Freiberg, Leipziger Straße 29, D-09596 Freiberg/Sa. Bundesrepublik
¨
¨
Deutschland, Germany
b Institut fur Angewandte Physik, Technische Universitat Bergakademie Freiberg, Bernhard-von-Cotta-Straße 4, D-09596 Freiberg/Sa. Bundesrepublik
¨
¨
Deutschland, Germany
Received 9 January 2002; received in revised form 12 February 2002; accepted 26 March 2002
Abstract
1
A series of substituted 1,2-N,N-dimethylaminomethylferrocenyl compounds were synthesized and characterized by H-NMR,
13C-NMR, 29Si-NMR, ESꢀ vis and 57Fe-Mossbauer spectroscopy. The new (R,S)-2-(N,N-dimethylaminomethyl)fer-
MS, IR, UVꢀ
rocenyl-(aryl)silanes (R,S)-FcNSiMen(C6H4X)m (nꢁ
Xꢁp-Br (14) were formed by the reaction of 2-dimethylaminomethylferrocenyllithium FcNLi (1) with chloroarylsilanes
ClSi(Me)n(C6H4X)m (nꢁ2ꢀ0, mꢁ1, Xꢁp-F (2); mꢁ2, Xꢁp-F (3); mꢁ3, Xꢁp-F (4) and mꢁ1, Xꢁp-Br (13)). The
/
/
¨
/
2ꢀ
/
0, mꢁ
/
1, Xꢁ
/
p-F (5); mꢁ
/
2, Xꢁ
/
p-F (6); mꢁ
/
3, Xꢁ
/
p-F (7) and mꢁ1,
/
/
/
/
/
/
/
/
/
/
/
/
treatment of 5, 6 and 14 with gaseous hydrogen chloride or picric acid resulted in the formation of the hydrochloride complexes 9,
10, 15 and the picrates 11, 12 and 16. The treatment of 14 with LiR or Mg and DMF resulted in the formation of (R,S)-2-(N,N-
dimethylaminomethyl)ferrocenyl(4-formylphenyl)dimethylsilane (18). The crystal structures of 7, 12 and 15 were determined by
single crystal X-ray analyses. 57Fe-Mossbauer spectroscopy gives evidence of a significant electronic coupling between the ferrocenyl
¨
unit and the organic acceptor moiety of the molecules in the ground state. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: 1,2-N,N-Dimethylaminomethylferrocenyl; Ferrocene; Mossbauer spectroscopy; Crystal structures; Silicon
¨
1. Introduction
compounds in non-linear optics have spurred research in
this area [10ꢀ13].
/
Due to the outstanding stability and the unique
redox-behavior the ferrocenyl unit is used in a vast
variety of synthesis [1]. Compared with organic non-
linear optics, the field of organometallic compounds
with non-linear optical properties is relatively young and
Very recently, functionalized ferrocene moieties like
the 1,2-N,N-dimethylaminomethylferrocenyl entity
(FcN) have become attractive units for the construction
of novel organometallic silane molecules [14]. Thus, the
treatment of chlorosilanes with 2-dimethylaminomethyl-
ferrocenyl lithium (FCNLi) (1) produces optically iso-
meric molecules such as, for example, (R,S)-
(FcN)2SiMe2. Optical activity (Scheme 1) and an inter-
esting redox behavior are the prominent features of such
FcN-substituted silanes.
With this in mind, we proceeded to synthesize and
characterize the new dipolar 2-(N,N-dimethylamino-
methyl)ferrocenyl-(4-aryl)silanes. Molecules of this type
permit different functional substituents to be introduced
at the silicon, especially acceptor groups, e.g. the
fluorophenyl entity. Some donor quality towards the
silicon atom may originate from the N,N-dimethyl-
aminomethyl substituent at the cyclopentadienyl ring
unexplored [2ꢀ4]. Dipolar ferrocene compounds are
/
investigated as compounds with potential non-linear
optical properties. Some ferrocenyl derivatives with
strong SHG-activity have already been reported [5ꢀ9].
/
The ability to functionalize both the ferrocene and the
silanyl moiety in ferrocenylsilanes permits the physical
properties to be tailored. Potential applications of such
* Corresponding author. Tel.: ꢂ
39-4058.
E-mail addresses: christian.beyer@chemie.tu-freiberg.de (C. Beyer),
uwe.boehme@chemie.tu-freiberg.de (U. Bohme).
/
49-3731-39-2050; fax: ꢂ49-3731-
/
¨
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 4 2 7 - 4

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C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
lographic study (Fig. 1). Clear homogeneous crystals of
up to 10 mm in size were grown.
Since our goal was to synthesize crystalline com-
pounds, we were looking for useful ways to prepare
derivatives of liquids 5 and 6. Thus, to exploit the N,N-
dimethylamino group at the ferrocenyl moiety, both
compounds were reacted with hydrogen chloride, L-
Scheme 1.
(ꢂ)-tartaric acid and picric acid. Hydrogen chloride
/
with 5 and 6 in n-pentane at 0 8C (after 30 min
treatment) gave fine yellow precipitates of the hydrogen
chloride adducts (9) and (10) (Scheme 3).
[15]. Furthermore, protonation of the nitrogen atom
seems to provide an additional option for arriving at
well-crystallized compounds.
The solids 9 and 10 do not crystallize very well. Both
compounds are moisture- sensitive and have to be
handled under anaerobic conditions. Single crystals of
sufficient quality could be isolated only from compound
10. The X-ray structure analysis delivered crystallo-
graphic data with final R-values of 12%.
The expected mixed-valence behavior of iron was
investigated by means of Mossbauer spectroscopy.
¨
2. Results and discussion
Treatment of 5 and 6 with chiral tartaric acid should
enable diastereomeric products to be formed which
would be highly desirable, but till now all of our trials
have failed. We are planning further experiments to
obtain ammonium salts with other chiral acids. The
reaction of 5 and 6 with the stronger picric acid
engendered the compounds 11 and 12 (Scheme 4).
Both of the ammonium picrates are stable in air and
well-crystallized. The molecular structure of 12 was
identified via X-ray structure analysis Figs. 6 and 8.
The p-bromophenyl substituent should be regarded as
an alternative to the fluorophenyl moiety for the
preparation of dipolar ferrocenylsilanes. A useful syn-
thetic sequence was found starting from (p-bromophe-
nyl)chlorodimethylsilane (13) [17]. The reaction of this
compound with FcNLi (1) in THF yielded the oily
2.1. Synthesis and properties
The
2-(N,N-dimethylaminomethyl)ferrocenyl(4-
fluorophenyl)silanes (5), (6) and (7) were synthesized
in a two-step procedure starting from (4-fluorphe-
nyl)magnesiumbromide. The treatment of the chloro(4-
fluorophenyl)silanes (2), (3) and (4) with 2-dimethyla-
minomethylferrocenyllithium [16] (FcNLi) (1) in THF
resulted in the formation of the silanes (5), (6) and (7)
(Scheme 2).
The compounds 5 and 6 are brown liquids and 7 is a
yellow solid. All three compounds possess single reso-
nance signals in the 29Si-NMR spectrum at ꢃ
/
7.8 (5), ꢃ
14.4 ppm (7), respectively. Compound 7
is highly soluble in organic solvents and stable in air.
/
11.0 (6) and ꢃ
/
Its crystallization from toluene resulted in the forma-
tion of yellow crystals suitable for an X-ray crystal-
brown (R,S)-2-(N,N-dimethylaminomethyl)ferroce-
nyl(p-bromophenyl)dimethylsilane (14) (Scheme 5). De-
Scheme 2.

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
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189
Fig. 1. View of two crystals of (R,S)-FcNSi(C6H4F)3 (7). Left and middle: polarized light; right: transparent prism.
Further preparative efforts were directed towards the
synthesis of the aldehyde (18). We are interested in using
this compound as an educt for the synthesis of
dicyanovinylidene derivatives. Three different proce-
dures (aꢀc in Scheme 5) were performed to transform
/
the bromo-phenyl group into the phenyl-aldehyde.
While such a transformation appears simple to achieve,
the task was more difficult than expected. The reaction
of 14 was performed with t-butyllithium in THF
(method a) as well as with magnesium in THF (method
b), followed by nucleophilic substitution of the carba-
nionic intermediate with dimethylformamide (DMF)
and finally a working up of the products mixture with
ammonium chloride in water. Both reaction sequences
gave a mixture of the desired aldehyde (18) and (R,S)-
FcNSiMe2C6H5 (19). The portion of 19 was below 10%
with both methods. The reaction with n-butyllithium in
Scheme 3.
THFꢀn-hexane (route c) followed by treatment with
/
DMF and ammonium chloride in water led to a mixture
of three reaction products: the aldehyde (18), the phenyl
silane (19) and the carbonic acid (20). We were able to
separate these products with an elegant procedure. The
carbonic acid (20) is insoluble in ether, whereas the other
two products dissolve easily. The preparation of a
bisulfite adduct [18,19] of the aldehyde (18) enabled us
to separate 18 from 19. The aldehyde (18) was regener-
ated from its bisulfite adduct by treating it with a diluted
solution of Na2CO3. We were able to isolate all three
reaction products (18), (19) and (20) as pure com-
pounds.
The transformation of 18 into its bisulfite adduct is an
effective method to separate the aldehyde from the
product mixture. Thereby, we were able to avoid the
chromatographic separation procedure and to reduce
the preparative efforts necessary to isolate these pro-
ducts. We will report in a forthcoming contribution
about the transformation into the 1,1-dicyanoethylene-
2-phenyl derivative.
Scheme 4.
rivatives of 14 with hydrogen chloride and picric acid
were prepared in the same manner used for the p-
fluorophenyl compounds. The hydrochloride (15) and
the picrate (16) are yellow crystalline products. An X-
ray structure analysis was done with a single crystal of
16. The structure was refined to an R-value of 10% due
to the disorder of the nitro groups at the picrate anion.
The reaction of 18 with picric acid in methanol gave
the well-crystallized picrate (21). It was characterized
with X-ray structure analysis.

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C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
HNMe2ꢂ-group. The methylene group of the ꢀ
/
CH2ꢀ
/
NMe2 unit is also affected by protonation. The meth-
ylene protons of the 2-(N,N-dimethylaminomethyl)fer-
rocenyl compounds give rise to two signals that appear
as doublets due to geminal 2J(1H,1H)-coupling at about
12 Hz. If the 2-(N,N-dimethylaminomethyl)ferrocenyl
compound is protonated, an additional coupling occurs
with the vicinal proton of the HNMe2ꢂ-group. These
coupling constants are in the range of 4ꢀ
of this vicinal coupling depends on the torsion angle Hꢀ
NMe2ꢂ ꢀ
Cꢀ [20]. The 2-(N,N-dimethylamino-
/
8 Hz. The value
/
3. Spectroscopic properties and solid state properties
/
/H
methyl)ferrocenyl(aryl)dimethylsilanes FcNSiMe2(C6-
H4X) exhibit two signals arising from the methyl groups
bound to the silicon atom between 0.5 and 1 ppm. Only
one signal emerges for the 2-(N,N-dimethylamino-
methyl)ferrocenyl(diaryl)-methylsilanes FcNSiMe(C6-
H4X)2.
3.1. NMR spectroscopy
The (R,S)-2-(N,N-dimethylaminomethyl)ferroceny-
l(aryl)silanes (R,S)-FcNSiMen(C6H4X)m (nꢁ
/
2ꢀ0,
/
mꢁ1) have some common spectroscopic features. Fig.
/
1
2 shows the H-NMR spectrum of compound 12 as a
The 13C-NMR spectra prove that pure compounds
were formed. All signals listed in the experimental part
were properly assigned. The presence of the para-fluoro
substituent in the compounds 5, 6, 7, 9, 10, 11, and 12
1
typical example. The H-NMR spectra are dominated
by an intensive singulet at 4.0ꢀ4.2 ppm that is caused by
/
the unsubstituted C5H5-ring. The three protons at the
1,2-substituted Cp-rings give rise to three signals be-
tween 4.0 and 5.2 ppm with the intensity ratio 1:1:1. The
provides the 13Cꢀ
/
19F-coupling constants as additional
signals appear mainly as multiplets due to J(1H,1H)-
3
analytic tool to assign the signals of the phenyl carbon
atoms. The coupling constants decrease as the line of
bonds increases between fluorine and the carbon atoms
4
and J(1H,1H)-coupling of the ring protons. From the
protons of the phenyl groups arise multiplets between
7.0 and 7.8 ppm. The resonances of the protons of the
dimethylamino groups occur at 1.7ꢀ2.0 ppm. The signal
pattern of the dimethylaminomethyl group changes
significantly when this group is protonated. The reso-
nance frequency shifts towards lower field and the signal
is split up into a doublet due to the coupling with the
additional attached proton at the nitrogen in the
1
in the following order: J(13C,19F)ꢁ
/
247ꢀ
/
250 Hz (ipso-
2
3
C), J(13C,19F)ꢁ
/
19ꢀ
/
20 Hz (ortho-C), J(13C,19F)ꢁ
/
7ꢀ
/
/
8 Hz (meta-C), J(13C,19F)ꢁ
/
3 Hz (para-C).
The 29Si-NMR spectra show one singulet at ꢃ
4
/
7 to ꢃ
/
11 ppm for the N,N-dimethylaminomethylferrocenylsi-
lanes. Mass spectra and elemental analyses complete the
characterization of the compounds.
Scheme 5.

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
/201
191
Fig. 2. 1H-NMR (CDCl3) of compound (R,S)-FcNSiMe(C6H4F)2ꢂ picrateꢃ (12).
3.2. Mossbauer spectroscopy
¨
3.3. Solid-state structures
Mossbauer spectroscopy is an excellent method for
¨
X-ray structure analyses of the compounds 7, 12 and
15 were performed in order to confirm the structure of
the prepared compounds. Crystal data and data collec-
tion parameters are given in Table 3, and a selection of
bond distances and angles are provided by Table 2.
investigating electronic charge transfer. By means of this
method, the electronic configuration of iron in ferrocene
derivatives was found to be 3d5.44 4s0.74 4p1.41 (FeII) [21].
The substitution of one hydrogen atom at the cyclo-
pentadienyl ring with electron acceptors should result in
a reduced electron density at the iron atom. This means
that the ferricinium ion (FeIII) is formed with the
electronic configuration 3d5 4s.
ORTEP diagrams of the structures are shown in Figs. 4ꢀ
/
8. From the fact that the compounds crystallize in
centrosymmetric space groups it is concluded that, both
isomers (R and S) are present in the structures. The
structures turn out to be very similar with respect to the
ferrocenyl unit. The distances between the iron atom
Table 1 demonstrates the results of the 57Fe-Moss-
¨
bauer spectra fit. The Mossbauer spectra recorded at
¨
different temperatures of compound 16 are shown in
Fig. 3. The isomer shifts of the spectra that were
observed correspond to the common values of FeII
and FeIII. All spectra display two doublets. The doublet
with large quadrupole splitting was created by the iron
in the ferrocene skeleton (FeII), the one with small
quadrupole splitting indicates ferricinium (FeIII). The
appearance of the Fe(III) signal in the spectra clearly
indicates the electron accepting character of the orga-
nosilanyl group attached to the ferrocene. Electron
and the cyclopentadienyl carbon atoms are in the range
˚
of 2.01ꢀ2.06 A. In all structures, the 1,2-substituted
/
ferrocenyl moiety adopts a nearly eclipsed conformation
of the cyclopentadienyl ring (see Fig. 4). This conforma-
tion is caused by the substituents at the cyclopentadienyl
ring, which force the neighboring ring into an eclipsed
position through steric interaction with the hydrogen
atoms at this ring.
The silicon atoms are tetrahedral coordinated in all
four molecules. Obviously, there is a slight distortion of
the tetrahedral angles due to steric interaction of the
phenyl groups and the ferrocenyl unit at the silicon
atom. Bonding interactions between silicon and nitrogen
transfer in the direction Cp0
density from the cyclopentadienyl ring, what is compen-
sated by the partial oxidation Fe(II)0Fe(III). The
observed charge transfer is a temperature dependent
intramolecular donorꢀacceptor interaction [12,21]. This
/
Si removes electron
/
in dimethylaminomethylferrocenylsilanes have been dis-
˚
SiCl3 with a distance of 2.682 A [15].
/
cussed for FcNꢀ
/
˚
type of interactions show an Arrhenius behavior. At 80
K the activation energy of the charge transfer hinders a
differentiation in the degree of oxidation of the different
moieties. Since all measurement results obtained are
reversible when the temperature is raised and lowered, a
partial oxidation in air could be excluded.
The distance SiÁ Á ÁN in 7 is 3.748 A, which is longer than
˚
the sum of the van der Waals radii (3.5 A). That means
there is no interaction between silicon and nitrogen in 7
in the solid state.
There is a significant hydrogen bridge in the (R,S)-
FcNSiMe(C6H4F)2 picrate (12) linking the hydrogen

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C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
Table 1
Mossbauer spectroscopic data
¨
Fig. 3. 57Fe-Mossbauer spectra of 16 at different temperatures (left 80 K, middle 175 K, right 298 K).
¨

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
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193
Table 2
Selected bond lengths (A) and bond angles (8)
˚
Bond lengths
Bond angles
(R,S)-FcNSi(C6H4F)3 (7)
SiꢀC(2)
1.858(4)
1.872(4)
1.875(4)
1.868(4)
1.355(4)
1.370(4)
1.359(5)
C(2)ꢀSiꢀC(14)
C(2)ꢀSiꢀC(20)
C(2)ꢀSiꢀC(26)
C(26)ꢀSiꢀC(14)
C(26)ꢀSiꢀC(20)
C(14)ꢀSiꢀC(20)
106.1(2)
113.1(2)
111.1(2)
107.9(2)
109.5(2)
108.8(2)
SiꢀC(14)
SiꢀC(20)
SiꢀC(26)
C(17)ꢀF(1)
C(23)ꢀF(2)
C(29)ꢀF(3)
(R,S)-FcNSiMe(C6H4F)2ꢂ picrateꢃ (12)
Si(1)ꢀC(2)
Si(1)ꢀC(14)
Si(1)ꢀC(15)
Si(1)ꢀC(21)
C(18)ꢀF(1)
C(24)ꢀF(2)
N(1)ꢀH(1)
H(1)....O(1)
1.867(3)
1.857(4)
1.876(3)
1.870(3)
1.360(4)
1.373(4)
0.93(2)
C(2)ꢀSi(1)ꢀC(15)
C(2)ꢀSi(1)ꢀC(21)
C(14)ꢀSi(1)ꢀC(2)
C(14)ꢀSi(1)ꢀC(21)
C(14)ꢀSi(1)ꢀC(15)
C(21)ꢀSi(1)ꢀC(15)
108.8(2)
107.6(2)
114.0(2)
109.9(2)
110.5(2)
105.6(2)
Fig. 5. ORTEP diagram of 7, 50% probability thermal ellipsoids,
hydrogen atoms omitted for clarity.
1.83(3)
(R,S)-FcNSiMe2(C6H4Br)ꢂ Clꢃ ×0.5H2O (15)
Si(1)ꢀC(2)
Si(1)ꢀC(14)
Si(1)ꢀC(15)
Si(1)ꢀC(16)
1.856(6)
1.868(8)
1.864(7)
1.889(7)
C(2)ꢀSi(1)ꢀC(15)
C(2)ꢀSi(1)ꢀC(14)
C(2)ꢀSi(1)ꢀC(16)
C(14)ꢀSi(1)ꢀC(16)
C(15)ꢀSi(1)ꢀC(16)
C(15)ꢀSi(1)ꢀC(14)
109.3(4)
113.9(3)
108.7(3)
109.5(3)
105.2(3)
109.8(4)
Br(1)ꢀC(19)
N(1)ꢀH(1)
H(1)Á Á ÁCl(1)
1.890(8)
1.03(2)
2.09(3)
atom of the dimethlyammonium group with the oxygen
˚
1.83 A).
A hydrogen bridge was also found in the structure of
15 between the dimethlyammonium group and the
Fig. 6. ORTEP diagram of the cation of 12, 50% probability thermal
ellipsoids.
atom of the picrate ion (H(1)Á Á ÁO(1)ꢁ
/
˚
2.09 A). The compound
chloride ion (H(1)Á Á ÁCl(1)ꢁ
/
15 crystallizes as a semi-hydrate with 0.5 mol water per
mol of dimethylamoniummethyl-ferrocenyl chloride;
therefore, the exact formula is given as: (R,S)-
FcNSiMe2(C6H4Br)ꢂ Clꢃ
0.5H2O. Because it was not
×
/
possible to localize the hydrogen atoms of the water
molecule from the X-ray data, Fig. 7 shows one isolated
Fig. 7. ORTEP diagram of 15×
/0.5 H2O, 50% probability thermal
ellipsoids.
oxygen atom (O(1)). The elemental analyses of 15 agree
with the proposed structure.
Due to thermal motion and/or disorder of the nitro
groups of the picrate anion, the picrate anion in 12
exhibits large atomic displacement parameters for the
oxygen atoms (see Fig. 8). X-ray structure analyses of
the compounds 10 and 16 revealed that the picrate
anions in both structures are heavily disordered leading
to final R-values of 13 and 10%, respectively. Because of
insufficient results, these structures will not discussed
Fig. 4. ORTEP diagram of 7, showing the conformation of the
cyclopentadienyl rings.

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C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
effervescence was observed. The solvents were distilled
once more and then stored in a sealed schlenk tube prior
to use. N,N-Dimethylformamide (DMF) was allowed to
˚
stand on 4 A molecular sieves and distilled from CaH2
under reduced pressure prior to use. 1,4-Dibromoben-
zene, 1-bromo-4-fluorobenzene and picric acid were
purchased from Fluka Chemie AG and used without
further purification. Synthesis of FcNLi (1) was done
according to the usual procedure [16].
NMR spectra were recorded on Bruker DPX 400 with
SiMe4 (TMS) CDCl3 or CD3CN as internal standard at
25 8C with 400.13 MHz for H-NMR, 100.62 MHz for
Fig. 8. ORTEP diagram of the picrate anion in 12, 50% probability
thermal ellipsoids.
1
13C-NMR and 79.49 MHz for 29Si-NMR. Signals are
noted as s (singlet), d (doublet), t (triplet), q (quartet), m
(multiplet), dd (doublet, doublet) and br (broad).
Elemental analyses were performed on a CHN-O-
RAPID (Hanau). Lower carbon content values than
real were measured due to the formation of silicon
carbide. Infrared spectra were recorded with a Carl Zeiss
here in more detail. Both structures are included in the
Cambridge Crystallographic Database.
Intermolecular distances between the fluorine atom
˚
and hydrogen atoms are in the range of 2.66ꢀ2.9 A,
/
which means they are above the sum of van der Waals
˚
radii (1.2ꢂ
/
1.35ꢁ2.55 A). These distances could signify
/
Jena Specord M82 IR instrument in the range 4000ꢀ400
/
weak hydrogen bonds [22], but it seems less likely that
these contacts have a substantial influence on the solid-
state structure types.
cmꢃ1 using the KBr disc method (additionally in
CH2Cl2 solution). Electronic spectra were obtained
with a M40-Zeiss UVꢀ
tra were obtained on a 70 eV Hewlettꢀ
Series II/5971 Series GCꢀMS system. ESꢀ
MeOH solution, positive ion detection mode) were
recorded on a 59987 A Series/5989-B-MS Hewlettꢀ
/
vis spectrometer. GCꢀ
Packard 5890
MS (ESI,
/
MS spec-
/
/
/
4. Conclusions
/
New dipolar N,N-dimethylaminomethylferrocenylsi-
lanes with organic acceptor groups were synthesized.
The final products are stable in air. Compound 7 with
three phenyl groups at silicon crystallizes well. X-ray
structure analyses of compounds with two or one phenyl
groups are not so easily accessible, therefore crystalline
derivatives were obtained by using hydrogen chloride or
Packard/Palo Alto, USA system.
¨
The 57Fe Mossbauer spectra were recorded with a
WISSEL instrument in transmission geometry at tem-
peratures of 80, 175, 298 K for 10, 12 and 16; at 80 and
295 K for 7 and 9. The g-ray source is 57Coꢀ
/Rh in a
rhodium matrix, 1.8 GBq. The spectra were fitted by
assuming Lorentz-profiles. Fit parameter: isomer shift
(d) relative to a-iron, quadrupole splitting (o), line width
(G) and intensity (I), velocity calibration with a-iron.
The intensities (I) of the partial spectra are the result of
the calculated area-parts of the sum spectra. Assuming
picric acid. 57Fe-Mossbauer spectroscopy gives evidence
¨
of a significant electronic coupling between the ferroce-
nyl unit and the organic acceptor moiety of the
molecules in the ground state. Such compounds should
have some special optical qualities. Therefore, NLO-
measurements with these molecules are planned to find
evidence of this behavior. We are currently synthesizing
compounds with other organic acceptor groups.
Furthermore, we are extending our strategy of deriva-
tization of the N,N-dimethylaminomethylferrocenylsi-
lanes with chiral acids, with the aim of separating the
diastereomers.
the same DebyeꢀWaller factor within a substance, the
/
calculated area-parts correspond to the quantity of the
phase portion in the sample. Due to the strong
temperature dependence of the DebyeꢀWaller factor
/
in the investigated samples, the quality of the 298 K
spectra of 7 and 9 are insufficient and no satisfactory
interpretation is possible.
5.1.1. Representative example synthesis of (4-
fluorophenyl)chlorodimethylsilane (2)
The synthetic procedures used to prepare compounds
5. Experimental
2ꢀ
/
4 and 5ꢀ7 are similar. A solution of 1-bromo-4-
/
5.1. General remarks
fluorobenzene (0.2 mol, 21.79 ml) in THF (100 ml) was
added slowly (1 h) to a suspension of magnesium (0.21
mol, 5.1 g) in THF (about 100 ml) activated by a crystal
of iodine. The mixture was stirred for 2 h and subse-
quently refluxed for 2 h. The solution was stirred at
room temperature (r.t.) overnight and the excess mag-
All the samples were prepared and handled under
Argon using dry glassware and dry solvents. Dry THF,
ether, n-pentane, n-hexane and toluene were repeatedly
distilled from fresh sodiumꢀbenzophenone until no
/

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
/201
195
nesium was removed. This Grignard reagent was added
slowly (1 h) to the solution of SiMe2Cl2 (0.29 mol, 35.0
ml) in THF (100 ml). The mixture was heated at reflux
for 5 h. The solvent was removed under vacuum and n-
hexane was added. The solution was filtered and washed
three times with n-hexane. The combined n-hexane
solutions were concentrated under vacuum. The residue
was distilled under reduced pressure and a colorless oil
eV): m/eꢁ
395 [M]ꢂ, 351 [FcCH2SiMe2C6H4F]ꢂ, 338
/
[FcSiMe2C6H4F]ꢂ, 284 [FcNSiMe]ꢂ, 242 [FcN]ꢂ, 242
[FcSiMe2]ꢂ, 227 [FcSiMe]ꢂ, 213 [FcSi]ꢂ, 199
[FcCH2]ꢂ, 121 [FeCp]ꢂ, 56 [Fe]ꢂ.
5.1.3. Synthesis of (bis-(4-
fluorophenyl))chloromethylsilane (3)
Based on the procedure that used for the synthesis of
2, compound 3 was prepared with 40 ml (0.367 mol) of
1-bromo-4-fluorobenzene, 9.72 g (0.4 mol) magnesium
and 200 ml THF. This Grignard reagent was added
slowly (1 h) to a solution of SiMeCl3 (0.19 mol, 22.4 ml)
was obtained (61ꢀ
52%). Spectroscopic data for 2: 1H-NMR (CDCl3ꢀ
TMS): 0.66 (s, SiMe2, 6H, 2J(1H, 29Si,)ꢁ
6.9 Hz),
7.60, 7.08 (AA?XX?, Ar-H, 2×2H), impurities: 0.46 (B
1%) ppm; 13C-NMR (CDCl3ꢀ
TMS): 2.2 (s, SiMe2,
1J(13C, 29Si,)ꢁ
59.9 Hz), 115.3 (d, C2 ortho,
2J(13C,19F)ꢁ20 Hz), 131.9 (d, C4 para, J(13C,19F)ꢁ
/
73 8C/6 Torr, isolated yield 19.6 g,
/
/
/
/
/
in THF (200 ml) at ꢃ
/
78 8C. The resulting colorless oil
/
was distilled under reduced pressure (111ꢀ
/
117 8C/4
4
/
/
Torr, isolated yield 24 g, 49%). This purification lead
1
to colorless oil (3). Spectroscopic data for 3: H-NMR
3
3.2 Hz), 135.3 (d, C3 meta, J(13C,19F)ꢁ
8.0 Hz), 164.3
/
(d, C1 ipso, 1J(13C,19F)ꢁ
(CDCl3ꢀ
/
250 Hz) ppm; 29Si-NMR:
(CDCl3ꢀ
Hz,), 7.09, 7.59 (m, AA?XX?, Ar-H, 2×
1.05 (B
1%) ppm; 13C-NMR (CDCl3ꢀ
SiMe, 1J(13C, 29Si)ꢁ
61.5 Hz), 115.5 (d, C2 ortho,
/
TMS): 0.91 (s, SiMe, 3H, 2J(1H,29Si)ꢁ
/
6.8
2H), impurities:
TMS): 1.1 (s,
1
/
TMS) 20.2 (s, SiMe2, J(29Si,13C)ꢁ
/
59.8 Hz),
/
impurities: 14.3 (ca. 1%) ppm; IR: nCꢀH
(m) 2912 (w) cmꢃ1, nCꢁC 1592 (s), 1501 (s) cmꢃ1
dCꢀH
1406 (w), 1388 (m), 1255 (s), 1236 (s) cmꢃ1
nCꢀF
1165 (s), 1111 (s) cmꢃ1, nCꢀH (para)ꢁ
824 (s), 808 (s), 790 (s) cmꢃ1, nSiꢀCl
cmꢃ1
MS (EI, 70 eV): m/eꢁ
[ClSiMeC6H4F]ꢂ,
153
ꢁ
/
3036 (w), 2961
/
/
ꢁ
/
,
,
/
ꢁ
/
2J(13C,19F)ꢁ
4J(13C,19F)ꢁ
3J(13C,19F)ꢁ
/
20.8
Hz),
Hz),
130.0
136.3
(d,
(d,
C4
C3
para,
meta,
ꢁ
/
/
844 (s),
515 (s), 487 (s)
188 [M]ꢂ, 173
[SiMe2C6H4F]ꢂ,
137
/3.2
ꢁ
/
1
/
8.0 Hz), 164.6 (d, C1 ipso, J(13C,19F)ꢁ
/
;
/
251.7 Hz) ppm; 29Si-NMR: (CDCl3ꢀ
SiMe), impurities: 7.4 (B1%) ppm; MS (EI, 70 eV):
m/eꢁ268 253 234
[M]ꢂ, [ClSi(C6H4F)2]ꢂ,
/TMS) 10.0 (s,
/
[SiMeC6H4F]ꢂ, 122 [SiC6H4F]ꢂ, 110 [MeC6H4F]ꢂ, 91
[MeC6H4]ꢂ; purity by GC 98%.
/
[ClSi(C6H4F)C6H4]ꢂ, 233 [SiMe(C6H4F)2]ꢂ, 218
[Si(C6H4F)2]ꢂ, 190 [(C6H4F)2]ꢂ, 173 [ClSiMeC6H4F]ꢂ,
, 151 [(C6H4)2]ꢂ, 123 [SiC6H4F]ꢂ, 110 [MeC6H4F]ꢂ, 91
[MeC6H4]ꢂ, 75 [C6H4]ꢂ; purity by GC 98.8%.
5.1.2. Representative example synthesis of (R,S)-
FcNSiMe2C6H4F (5)
A suspension of FcNLi (1) (4.5 g, 18 mmol) and THF
(70 ml) was added slowly drop-wise to a stirred solution
of 2 (3.6 g, 19 mmol) in 40 ml of n-pentane at ꢃ
/
78 8C.
5.1.4. Synthesis of (R,S)-FcNSiMe(C6H4F)2 (6)
The procedure followed was that used for the synth-
esis of compound 5. A suspension of FcNLi (1) (4.3 g,
17.2 mmol) and THF (50 ml) was added slowly drop-
wise to a stirred solution of (3) (4.85 g, 18 mmol) in 30
The mixture was warmed up slowly to ambient tem-
perature and was stirred over night at r.t. Subsequently
the solvent and unreacted 2 was stripped off, and the
dark viscous product was dissolved with n-pentane and
filtered. The solvent was removed under reduced pres-
sure, and a brown oil 5 was obtained. Spectroscopic
ml of n-pentane at ꢃ
/
78 8C. The solvent was removed
under reduced pressure and a brown oil (6) was
data for 5: 1H-NMR (CDCl3ꢀ
0.61 (s, SiMe, 3H), 1.96 (s, NMe2, 6H), 2.89 (d, NCH2,
1H, 2J(1H,1H)ꢁ
12.4 Hz), 3.39 (d, NCH2, 1H,
2J(1H,1H)ꢁ
12.4 Hz), 4.00 (s, Cp, 1H), 4.07 (s, Cp,
5H), 4.25 (t, Cp, 1H, J(1H,1H)ꢁ
1H), 7.0, 7.56 (AA?XX?, Ar-H, 2×
2H) ppm; 13C-NMR
(CDCl3ꢀTMS): ꢃ1.26 (s, SiMe), ꢃ0.96 (s, SiMe), 44.7
/TMS): 0.54 (s, SiMe, 3H),
obtained. Spectroscopic data for 6: H-NMR (CDCl3ꢀ
TMS): 0.90 (s, SiMe, 3H, 2J(1H,29Si)ꢁ
6.6 Hz,), 1.89 (s,
NMe2, 6H), 2.79 (d, NCH2, 1H, J(1H,1H)ꢁ
12.4 Hz),
3.20 (d, NCH2, 1H, 2J(1H,1H)ꢁ
12.6 Hz), 3.93 (dd, Cp,
1H), 4.03 (s, Cp, 5H), 4.30 (t, Cp, 1H, J(1H,1H)ꢁ
Hz), 4.38 (dd, Cp, 1H), 7.02, 7.54 (m, AA?XX?, Ar-H, 2×
2H) ppm; 13C-NMR (CDCl3ꢀ
TMS): ꢃ2.2 (s, SiMe,
1J(13C, 29Si)ꢁ
56.7 Hz), 44.7 (s, NMe2), 59.2 (NCH2),
/
1
/
2
/
/
/
/
3
3
/2.3 Hz), 4.31 (s, Cp,
/2.4
/
/
/
/
/
/
/
(s, NMe2), 59.4 (NCH2), 68.8 (Cp), 69.8 (CH, Cp), 70.0
(C, Cp), 73.8 (CH, Cp), 74.8 (CH, Cp), 90.2 (C, Cp),
/
68.5 (C, Cp), 70.0 (Cp), 70.2 (CH, Cp), 74.2 (CH, Cp),
75.7 (CH, Cp), 90.5 (C, Cp), 114.5 (d, C2 ortho,
2
114.4 (d, C2 ortho, J(13C,19F)ꢁ
/
19.2 Hz), 135.5 (d, C4
para, 4J(13C,19F)ꢁ
3J(13C,19F)ꢁ7.2 Hz), 163.6 (d, C1 ipso, J(13C,19F)ꢁ
247.7 Hz) ppm; 29Si-NMR: (CDCl3ꢀ
TMS) ꢃ7.8 (s,
SiMe2) ppm; IR (CH2Cl2): nCꢀH 3062 (w), 2995 (w)
2928 (w) cmꢃ1, nCꢁC 1587 (w), 1500 (w) cmꢃ1
dCꢀH 1421 (w), 1264 (s), nCꢀF 1167 (w), 1102 (s)
cmꢃ1, nCꢀH (para)ꢁ742 (s), 706 cmꢃ1; GCꢀ
MS (EI, 70
/
3.2 Hz), 135.7 (d, C3 meta,
2J(13C,19F)ꢁ
/
20 Hz), 114.6 (d, C2 ortho, J( C, F)ꢁ
20.0 Hz), 133.2 (d, C4 para, 4J(13C,19F)ꢁ
3.2 Hz), 133.4
4.0 Hz), 137.0 (d, C3 meta,
/
2
13 19
?
1
/
/
/
4
13 19
?
/
/
(d, C4 para, J( C, F)ꢁ
3J(13C,19F)ꢁ
8.0 Hz), 137.1 (d, C3 meta, J( C, F)ꢁ
8.0 Hz), 163.7 (d, C1 ipso, 1J(13C,19F)ꢁ
248.5 Hz), 163.7
247.7 Hz) ppm; 29Si-NMR:
11.0 (s, SiMe) ppm.
/
3
13 19
?
ꢁ
/
/
/
ꢁ
/
,
/
1
13 19
?
ꢁ
/
ꢁ
/
(d, C1 ipso, J( C, F)ꢁ
/
/
/
(CDCl3ꢀTMS) ꢃ
/
/

196
C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
5.1.5. Synthesis of (Tris-(4-fluorophenyl))chlorosilane
(4)
5.1.7. Synthesis of (4-bromophenyl)chlorodimethylsilane
(13)
Synthesis of 13 was performed according to that one
used for the synthesis of 2 with 35 g (0.148 mol) of 1,4-
dibromobenzene, 4.1 g (0.168 mol) magnesium and 200
ml THF. This Grignard reagent was added slowly (1 h)
to a solution of SiMe2Cl2 (0.228 mol, 27.45 ml) in THF
(200 ml) at 0 8C. The resulting colorless oil was distilled
The synthesis procedure of 4 was based on that one
used for the synthesis of compound (4-fluorophe-
nyl)chlorodimethylsilane (2) with 60 ml (0.55 mol) of
1-bromo-4-fluorobenzene, 19 g (0.78 mol) magnesium
and 200 ml THF. This Grignard reagent was added
slowly (1 h) to a solution of SiCl4 (0.195 mol, 22.4 ml) in
under reduced pressure (70ꢀ
yield 11.1 g, 30%). This purification gave a colorless oil
(13). Spectroscopic data for 13: 1H-NMR (CDCl3ꢀ
TMS): 0.66 (s, SiMe2, 6H), 7.503 (AA?XX?, Ar-H, 2×
2H, 3J(1H,1H)ꢁ
8.40 Hz), impurities: 0.811, 0.461,
0.308 (B TMS): 2.0 (s,
1%) ppm; 13C-NMR (CDCl3ꢀ
/
76 8C/1ꢀ
/
2 Torr, isolated
THF (200 ml) at ꢃ
was distilled under reduced pressure (192ꢀ
/
78 8C. The resulting colorless oil
194 8C/2
/
/
Torr). This purification lead to white crystals (4)
/
(isolated yield 38 g, 59%). Spectroscopic data for 4:
1H-NMR (CDCl3ꢀ
2×
2H), ppm; 13C-NMR (CDCl3ꢀ
ortho, 2J(13C,19F)ꢁ
20.8 Hz), 128.2 (d, C4 para,
4J(13C,19F)ꢁ
4.0 Hz), 137.4 (d, C3 meta,
3J(13C,19F)ꢁ8.0 Hz), 164.8 (d, C1 ipso, J(13C,19F)ꢁ
252.5 Hz) impurities: 29.3, 31.0, 63.0 (B
3%) ppm; 29Si-
NMR: (CDCl3ꢀTMS) 1.0 (s, SiPhF), impurities: ꢃ13.5,
13.7 (B3%) ppm.
/
TMS): 7.10, 7.59 (m, AA?XX?, Ar-H,
TMS): 115.7 (d, C2
/
/
/
/
/
SiMe2), 125.3 (s, C4 para), 131.3 (s, C2 ortho), 134.7 (s,
C3 meta), 135.0 (s, C1 ipso), impurities:133.1 (1,4-
dibromobenzene), 160.0, 62.2, 33.5, 30.5, 29.2 ppm;
/
/
1
/
/
29Si-NMR: (CDCl3ꢀ
14.3, ꢃ0.6 (ca. 2%) ppm.
The third fraction of the distillation under vacuum
/TMS) 20.5 (s, SiMe2), impurities:
/
/
/
/
/
was identified as 1,4-bis(dimethylchlorosilyl)benzene
(17). Spectroscopic data for 17: 1H-NMR (C6D6ꢀ
The first fraction of the distillation under vacuum was
identified as 4,4?-difluorobiphenyl (8). Spectroscopic
/
TMS): 0.42 (s, SiMe2, 6H), 7.50 (AA?XX?, Ar-H, 2×
2H), impurities: 0.31, 0.35, 0.56 (B
2%) ppm; 13C-
TMS): 1.8 (s, SiMe2, J(13C, 29Si)ꢁ
59.4
Hz)), 131.5, 132.9, 135.0, 138.7, impurities: 133.0 (1,4-
dibromobenzene), 0.9, 2.6 ppm; 29Si-NMR: (C6D6ꢀ
/
data for 8: 1H-NMR (CDCl3ꢀ
/
TMS): 7.11, 7.48 (m,
TMS):
/
AA?XX?, Ar-H, 2×
/
4H), ppm; 13C-NMR (CDCl3ꢀ
/
1
NMR (C6D6ꢀ
/
/
2
13 19
?
115.7 (d, C2,C2 ortho, J( C, F)ꢁ
/
21.5 Hz), 128.6 (d,
?
C3, C3 meta, 3J(13C,19F)ꢁ
para, 4J(13C,19F)ꢁ
1J(13C,19F)ꢁ
246.1 Hz) ppm.
/8.0 Hz), 136.4 (d, C4, C4
?
/
1
TMS) 20.3 (s, SiMe2, J(13C, 29Si)ꢁ
/
59.3 Hz)), impu-
?
/3.2 Hz), 162.4 (d, C1, C1 ipso,
262 [M]ꢂ,
/
rities: 16.8, ꢃ0.5 ppm; MS (EI, 70 eV): m/eꢁ
/
/
247 [ClSiMe2(C6H4)SiMeCl]ꢂ, 227 [ClSiMe2(C6H4)-
SiMe2]ꢂ, 211 [ClSiMe2(C6H4)SiMe]ꢂ, 197 [ClSiMe2-
(C6H4)Si]ꢂ, 181 [ClSiMe(C6H4)Si]ꢂ, 175 [SiMe2-
(C6H4)SiMe]ꢂ, 153 [ClSiMe(C6H4)]ꢂ, 133 [SiMe2-
(C6H4)]ꢂ, 119 [SiMe(C6H4)]ꢂ, 105 [Me2(C6H4)]ꢂ, 91
[MeC6H4]ꢂ.
5.1.6. Synthesis of (R,S)-FcNSi(C6H4F)3 (7)
Compound 7 was synthesized analogously to the
procedure used for the synthesis for (R,S)-FcNSi-
Me2C6H4F (5). A suspension of FcNLi (1) (5.97 g,
23.95 mmol) and THF (50 ml) was added slowly drop-
wise to a stirred solution of 4 (8.348 g, 20 mmol) in 30 ml
of n-pentane at 0 8C. The solvent was removed under
reduced pressure. Finally a yellow solid (7) remained.
The product was recrystallized from PhMe to yellow
crystals of 7. Spectroscopic data for 7: 1H-NMR
5.1.8. Synthesis of (R,S)-FcNSiMe2C6H4Br (14)
Synthesis of 14 was done on the same pathway as in
case of compound 5. A suspension of FcNLi (1) (4.3 g,
17.2 mmol) and THF (50 ml) was added slowly drop-
wise to a stirred solution of 13 (4.85 g, 18 mmol) in 30 ml
of n-pentane at ꢃ
under reduced pressure and gave a brown oil (14).
Spectroscopic data for 14: 1H-NMR (CDCl3ꢀ
TMS):
0.53 (s, SiMe, 3H, 2J(1H,29Si)ꢁ
6.60 Hz,), 0.60 (s, SiMe,
3H, 2J(1H,29Si)ꢁ
6.58 Hz,), 1.95 (s, NMe2, 6H), 2.86 (d,
NCH2, 1H, J(1H,1H)ꢁ
12.44 Hz), 3.41 (d, NCH2, 1H,
2J(1H,1H)ꢁ
12.44 Hz), 3.99 (dd, Cp, 1H), 4.07 (s, Cp,
5H) 4.25 (t, Cp, 1H, J(1H,1H)ꢁ
1H), 7.44, (m, AA?XX?, Ar-H, 2×
(CDCl3ꢀTMS): ꢃ1.5 (s, SiMe), ꢃ
/
78 8C. The solvent was removed
(CDCl3ꢀ
H, 2J(1H,1H)ꢁ
2J(1H,1H)ꢁ
12.4 Hz), 4.02 (Cp, 5H), 4.05 (s, Cp, 1H),
4.38 (s, Cp, 1H), 4.44 (s, Cp, 1H), 7.08, 7.61 (m,
AA?XX?, Ar-H, 2×
2H) ppm; 13C-NMR (CDCl3ꢀ
/TMS): 1.76 (s, NMe2, 6H), 2.70 (d, NCH2,
/12.4 Hz), 2.95 (d, NCH2, H,
/
/
/
/
2
/
/
/
TMS): 44.7 (s, NMe2), 58.8 (NCH2), 65.9 (C, Cp),
/
3
69.3 (Cp), 70.6 (CH, Cp), 74.4 (CH, Cp), 76.5 (CH, Cp),
/
2.0 Hz), 4.30 (dd, Cp,
2H) ppm; 13C-NMR
1.1 (s, SiMe), 44.7 (s,
90.9 (C, Cp), 114.8 (d, C2 ortho, 2J(13C,19F)ꢁ
/19.2 Hz),
/
4
131.1 (d, C4 para, J(13C,19F)ꢁ
meta, 3J(13C,19F)ꢁ
1J(13C,19F)ꢁ
TMS) 14.4 (s, SiPhF) ppm; Anal. Calc. for
/4.0 Hz), 138.2 (d, C3
/
/
/
/7.2 Hz), 163.9 (d, C1 ipso,
NMe2), 59.4 (NCH2), 68.8 (Cp), 69.5 (C, Cp), 69.8 (CH,
Cp), 73.9 (CH, Cp), 74.8 (CH, Cp), 90.2 (C, Cp), 123.3
(s, C4 para), 130.4 (s, C2 ortho), 135.6 (s, C3 meta), 139.0
/
249.3 Hz) ppm; 29Si-NMR: (CDCl3ꢀ
/
ꢃ
/
(s, C1 ipso) ppm; 29Si-NMR: (CDCl3ꢀ
/
TMS) ꢃ
/
7.3 (s,
C31H28F3FeNSi: C, 67.02; H, 5.08; N, 2.52. Found: C,
66.62; H, 5.31; N, 2.62%.
1
SiMe2, J(29Si,13C)ꢁ
/
61.23 Hz), impurities: ꢃ0.63 (B
/
/

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
/201
197
12%) ppm; ESꢀ
/
MS (EI, 70 eV, pos., MeCNꢀ
/
80.7 (C, Cp), 115.9 (d, C2 ortho, 2J(13C,19F)ꢁ
/
19.6 Hz),
4
CH3COOH): m/eꢁ
/
455 ([M]ꢂꢃ
/
1, cation), 412
[FcCH2SiMe2C6H4Br]ꢂ, 332 [FcCH2SiMe2C6H4]ꢂ,
257 [FcCH2SiMe2]ꢂ, 198 [FcCH2]ꢂ.
136.0 (d, C4 para, J(13C,19F)ꢁ
meta, 3J(13C,19F)ꢁ
1J(13C,19F)ꢁ
C, NO2Ar) ppm; 29Si-NMR: (CD3CNꢀ
SiMe2) ppm; ESꢀMS (EI, 70 eV, pos., MeCN): m/eꢁ
395 ([M]ꢂꢃ1, cation), 350 [FcCH2SiMe2C6H4F]ꢂ, 299
/3.2 Hz), 137.1 (d, C3
/
7.6 Hz), 164.7 (d, C1 ipso,
246.5 Hz), 126.7, 127.6, 143.1, 162.7 (6×
TMS) ꢃ8.1 (s,
/
/
/
/
5.2. Synthesis of 1,2-N,N-
/
/
dimethylaminomethylferrocenyl picrates
/
[FcNSiMe2]ꢂ, 198 [FcCH2]ꢂ; Anal. Calc. for
C27H29FFeN4O7Si: C, 51.92; H, 4.68; N, 8.97. Found:
C, 51.77; H, 4.91; N, 8.85%.
5.2.1. Synthesis of (R,S)-FcNSiMe2C6H4Br picrate
(16)
An ethanolic solution of picric acid was added drop-
wise to a solution of 14 (1 g, 2.19 mmol) in EtOH (25
ml). The suspension was warmed up for 3 min and
filtrated after ended precipitate formation. The resulting
yellow precipitate was washed with cold EtOH and
Et2O. The yellow solid was dissolved in hot EtOH and
5.2.3. Synthesis of (R,S)-FcNSiMe(C6H4F)2 picrate
(12)
Synthesis of compound 12 was done analogously to
that one of 16 with 1 g (2.10 mmol) of 6 in EtOH (25
1
ml). Spectroscopic data for yellow crystals of 12: H-
filtrated. The product was recrystallized from EtOHꢀ
/
NMR (CDCl3ꢀ
/
TMS): 1.0 (s, SiMe, 3H), 2.28 (d, br,
NMe, 3H, J(1H,1H)ꢁ
4.4 Hz,), 2.48 (d, br, NMe, 3H,
3J(1H,1H)ꢁ
4.0 Hz,), 3.39 (dd, br, NCH2, 1H,
2J(1H,1H)ꢁ
NCH2, 1H, 2J(1H,1H)ꢁ
3
MeCN 1:1 to yellow crystals of 16. Spectroscopic data
1
/
for 16: H-NMR (CDCl3ꢀ/TMS): 0.53 (s, SiMe, 3H),
/
3
0.78 (s, SiMe, 3H), 2.28 (s, NMe, 3H), 2.48 (s, NMe,
/
13.3 Hz, J(1H,1H)ꢁ
/
6.9 Hz), 4.47 (d, br,
2
3H), 3.66 (d, NCH2, 1H, J(1H,1H)ꢁ
NCH2, 1H, 2J(1H,1H)ꢁ
13.0 Hz), 4.25 (s, Cp, 5H), 4.33
(s, Cp, 1H), 4.58 (t, Cp, 1H), 4.74 (s, Cp, 1H), 7.35 (m,
AA?XX?, Ar-H, 2× 8.0 Hz), 7.48 (m,
H, 3J(1H,1H)ꢁ
AA?XX?, Ar-H, 2× 8.0 Hz), 8.90 (s,
H, 3J(1H,1H)ꢁ
NO2Ar-H, 2 H), 10.8 (br, Hꢀ
Nꢂ, 1 H) ppm; 13C-
NMR (CDCl3ꢀTMS): ꢃ1.3 (s, SiMe), ꢃ0.1 (s, SiMe),
/
13.4 Hz), 4.45 (d,
/
12.4 Hz), 4.17 (dd, Cp, 1H,
4
/
3J(1H,1H)ꢁ
5H), 4.60 (t, Cp, 1H, 3J(1H,1H)ꢁ
1H, 3J(1H,1H)ꢁ
7.47ꢀ7.58 (m, AA?XX?, Ar-H, 2×
H, 2 H), 10.73 (br, Hꢀ
Nꢂ, 1 H) ppm; 13C-NMR
(CDCl3ꢀTMS): ꢃ1.0 (s, br, SiMe), 40.7 (s, NMe), 43.8
/
2.4 Hz, J(1H,1H)ꢁ
/1.1 Hz), 4.22 (s, Cp,
/2.4 Hz), 4.85 (dd, Cp,
/
/
/
2.2 Hz, 4J(1H,1H)ꢁ
/1.1 Hz), 7.12,
/
/
/
/2H), 8.90 (s, NO2Ar-
/
/
/
/
/
/
/
40.8 (br, NMe2), 43.3 (br, NMe2), 58.0 (NCH2), 69.7
(Cp), 70.6 (C, Cp), 73.6 (CH, Cp), 74.6 (CH, Cp), 76.5
(CH, Cp), 78.9 (C, Cp), 124.4 (s, C4 para), 131.3 (s, C2
ortho), 135.2 (s, C3 meta), 137.5 (s, C1 ipso) 126.6, 128.3,
(s, NMe), 57.8 (NCH2), 69.3 (C, Cp), 69.9 (Cp), 73.9
(CH, Cp), 74.7 (CH, Cp), 77.3 (CH, Cp), 79.4 (C, Cp),
2
115.4 (d, C2 ortho, J(13C,19F)ꢁ
/
20.0 Hz), 115.8 (d, C2
?
ortho, 2J(13C,19F)ꢁ
4J(13C,19F)ꢁ
3.2 Hz), 136.9 (d, C3 meta, J(13C,19F)ꢁ
/
20.0 Hz), 131.2 (d, C4 para,
4
13 19
141.7, 162.2 (6×
TMS) ꢃ7.7 (s, SiMe2) ppm; ESꢀ
MeCN): m/eꢁ457
([M]ꢂ,
/
C, NO2Ar) ppm; 29Si-NMR: (CDCl3ꢀ
MS (EI, 70 eV, pos.,
cation), 411
/
/
3.2 Hz), 131.7 (d, C4 para, J( C, F)ꢁ
/
?
3
/
/
/
8.0 Hz), 137.0
3
13 19
?
/
(d, C3 meta, J( C, F)ꢁ
1J(13C,19F)ꢁ
1J(13C,19F)ꢁ
C, NO2Ar) ppm; 29Si-NMR: (CDCl3ꢀ
SiMe2) ppm; ESꢀMS (EI, 70 eV, pos., MeCN): m/eꢁ
475 ([M]ꢂꢃ1, cation), 431 [FcCH2SiMe2C6H4F]ꢂ, 335
/
7.2 Hz), 164.1 (d, C1 ipso,
[FcCH2SiMe2C6H4Br]ꢂ, 332 [FcCH2SiMe2C6H4]ꢂ,
273 [FcNSi]ꢂ, 198 [FcCH2]ꢂ; Anal. Calc. for
C27H29BrFeN4O7Si: C, 47.31; H, 4.26; N, 8.18. Found:
C, 47.45; H, 4.38; N, 8.09%.
/
250.9 Hz), 164.2 (d, C1 ipso,
?
/
251.7 Hz), 126.6, 128.4, 141.8, 162.1 (6×
/
/
TMS) ꢃ11.6 (s,
/
/
/
/
5.2.2. Synthesis of (R,S)-FcNSiMe2C6H4F picrate (11)
Synthesis of compound 16 was done based on that
one of 16 with 1 g (2.53 mmol) of 5 in EtOH (25 ml).
[FcCH2SiMe2]ꢂ, 199 [FcCH2]ꢂ, 122 [FeCp]ꢂ; Anal.
Calc. for C32H30F2FeN4O7Si: C, 54.55; H, 4.29; N, 7.95.
Found: C, 54.67; H, 4.38; N, 7.99%.
The product was recrystallized from hot acetoneꢀ
/
i-
propanol 1:3 to yellow crystals of 11. Spectroscopic data
5.3. Synthesis of 1,2-N,N-
dimethylaminomethylferrocenyl hydrochlorides
1
for 11: H-NMR (CD3CNꢀ
0.76 (s, SiMe, 3H), 2.40 (br, NMe2, 6H), 3.66 (d, NCH2,
1H, 2J(1H,1H)ꢁ
13.6 Hz), 4.37 (d, NCH2, 1H,
2J(1H,1H)ꢁ
13.7 Hz), 4.25 (s, Cp, 5H), 4.35 (dd, Cp,
/TMS): 0.54 (s, SiMe, 3H),
/
5.3.1. Synthesis of (R,S)-FcNSiMe2C6H4Br×
/
HCl×
/
0.5
/
H2O (15)
3
4
1H, J(1H,1H)ꢁ
Cp, 1H, 3J(1H,1H)ꢁ
3J(1H,1H)ꢁ2.5 Hz, 4J(1H,1H)ꢁ
(m, AA?XX?, Ar-H, 2×2H), 8.68 (s, NO2Ar-H, 2 H),
10.67 (br, Hꢀ
Nꢂ, 1 H) ppm; 13C-NMR (CD3CNꢀ
TMS): ꢃ1.1 (s, SiMe), 0.1 (s, SiMe), 42.9 (s, br,
/
2.2 Hz, J(1H,1H)ꢁ
2.4 Hz), 4.71 (dd, Cp, 1H,
1.1 Hz), 7.08, 7.58
/
1.1 Hz), 4.56 (t,
A solution of 20% HCl was added slowly to a solution
of 2.1 g (4.6 mmol) of 14 in 20 ml toluene for 30 min.
The mixture was stirred for 2 days at r.t. The resulting
fine yellow precipitate was washed with n-pentane and
Et2O. Then it was dissolved in hot MeCN and filtered.
The clear yellow solution was cooled slowly at ꢃ
The product recrystallized to yellow crystals of 15.
Spectroscopic data for 15: 1H-NMR (CDCl3ꢀ
TMS):
/
/
/
/
/
/
/
/
20 8C.
NMe), 43.5 (s, NMe2), 58.9 (NCH2), 70.6 (Cp), 72.1
(C, Cp), 74.1 (CH, Cp), 75.5 (CH, Cp), 77.5 (CH, Cp),
/

198
C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
0.53 (s, SiMe, 3H), 0.75 (s, SiMe, 3H), 2.14 (br, NMe,
3H), 2.42 (br, NMe, 3H), 3.54 (d, NCH2, 1H,
53.91; H, 6.68; N, 2.99. Found: C, 54.25; H, 6.49; N,
3.13%.
2J(1H,1H)ꢁ
/
13.16 Hz), 4.36 (d, NCH2, 1H,
13.92 Hz), 4.22 (s, Cp, 5H), 4.31 (d, Cp,
2J(1H,1H)ꢁ
/
5.3.3. Synthesis of (R,S)-FcNSiMe(C6H4F)2×
/
HCl
1H), 4.37 (s, Cp, 1H), 4.61 (t, Cp, 1H, J(1H,1H)ꢁ
/
2.2
8.0 Hz),
8.0 Hz),
Nꢂ, 1 H) ppm; 13C-NMR (CDCl3ꢀ
TMS):
1.1 (s, SiMe), ꢃ0.1 (s, SiMe), 39.8 (br, NMe2), 42.8
(10)
3
Hz), 7.34 (m, AA?XX?, Ar-H, 2×
7.47 (m, AA?XX?, Ar-H, 2×
H, 3J(1H,1H)ꢁ
11.96 (br, Hꢀ
/
H, 3J(1H,1H)ꢁ
/
The procedure to synthesize compound 10 was the
same as used for 9 with 3.0 g (6.31 mmol) of 6 in 50 ml
n-pentane. The product was recrystallized from hot
/
/
/
/
ꢃ
/
/
EtOHꢀ
data for 10: H-NMR (CD3CNꢀ
3H, 2J(1H,29Si)ꢁ
6.4 Hz,), 1.98 (d, NMe, 3H,
3J(1H,1H)ꢁ5.12 Hz), 2.42 (d, NMe, 3H, J(1H,1H)ꢁ
4.96 Hz), 3.30 (dd, NCH2, 1H, 2J(1H,1H)ꢁ
13.7 Hz,
3J(1H,1H)ꢁ
8.08 Hz), 4.31 (dd, NCH2, 1H,
2J(1H,1H)ꢁ13.8 Hz, 3J(1H,1H)ꢁ
3.0 Hz), 4.11 (dd,
Cp, 1H), 4.19 (s, Cp, 5H), 4.61 (t, Cp, 1H,
3J(1H,1H)ꢁ
2.4 Hz), 5.21 (dd, Cp, 1H), 7.16, 7.60 (m,
AA?XX?, Ar-H, 2×
2H) ppm; 13C-NMR (CD3CNꢀ
TMS): ꢃ1.3 (s, SiMe), 40.2 (s, NMe2), 43.7 (s, NMe2),
/
MeCN to yellow crystals of 10. Spectroscopic
1
(br, NMe2), 57.0 (NCH2), 69.6 (Cp), 70.4 (C, Cp), 73.6
(CH, Cp), 75.6 (CH, Cp), 76.3 (CH, Cp), 78.8 (C, Cp),
124.4 (s, C4 para), 131.3 (s, C2 ortho), 135.2 (s, C3 meta),
/
TMS): 1.02 (s, SiMe,
/
3
/
/
137.5 (s, C1 ipso) ppm; 29Si-NMR: (CDCl3ꢀ
/
TMS) ꢃ
55.40, Hz) ppm; ESꢀMS (EI,
70 eV, pos., MeOH): m/eꢁ 2, cation), 412
455 ([M]ꢂꢃ
[FcCH2SiMe2C6H4Br]ꢂ, 377 [FcNSiMe2C6H4]ꢂ, 304
[FcNSiMe2]ꢂ, 239 [FcN]ꢂ, 948 FcNSiMe2C6H4Br×
HClꢂ
cation [M]ꢂ; Anal. Calc. for C21H28BrClFe-
/
7.7
/
1
(s, SiMe2, J(29Si,13C)ꢁ
/
/
/
/
/
/
/
/
/
/
/
/
NO0.5Si: C, 50.27; H, 5.62; N, 2.79. Found: C, 50.03;
H, 5.77; N, 2.88%.
/
57.4 (NCH2), 69.8 (C, Cp), 70.8 (Cp), 74.1 (CH, Cp),
76.6 (CH, Cp), 77.8 (CH, Cp), 81.6 (C, Cp), 115.9 (d, C2
ortho, 2J(13C,19F)ꢁ
/
19.9 Hz), 116.2 (d, C2 ortho,
?
5.3.2. Synthesis of (R,S)-FcNSiMe2C6H4F×
/
HCl (9)
2J(13C,19F)ꢁ
4J(13C,19F)ꢁ
4.0 Hz), 138.3 (d, C3 meta, J(13C,19F)ꢁ
/20.0
Hz),
133.4
(d,
C4
para,
4
13 19
?
A stream of dry gaseous hydrogen chloride was
flushed slowly through the solution of 2.97 g (7.5
mmol) of 5 in 70 ml n-pentane at 0 8C for 30 min.
The mixture was warmed up to ambient temperature
and stirred over night at r.t. After that all the unreacted
HCl was removed from the flask, and the precipitate
was filtered off. The resulting fine yellow precipitate was
washed with a little bit of n-pentane, dried in a stream of
argon and under oil-pump vacuum to afford 3.1 g (95%)
/
3.2 Hz), 133.5 (d, C4 para, J( C, F)ꢁ
/
3
/
8.0 Hz), 138.4
3
13 19
?
(d, C3 meta, J( C, F)ꢁ
1J(13C,19F)ꢁ
1J(13C,19F)ꢁ
TMS)ꢃ11.3 (s, SiMe) ppm; ESꢀ
MeOH): m/eꢁ476
([M]ꢂ,
[FcCH2SiMe(C6H4F)2]ꢂ, 334 [FcCH2SiMe(C6H4F)]ꢂ,
199 986 HClꢂ
[FcCH2]ꢂ,
[FcNSiMe(C6H4F)2×
cation]ꢂ; Anal. Calc. for C26H28ClF2FeNSi: C, 61.00;
H, 5.51; N, 2.74, respectively, 10×H2O C26H30ClF2Fe-
/
7.6 Hz), 164.9 (d, C1 ipso,
?
/
247.3 Hz), 165.1 (d, C1 ipso,
/
247.7 Hz) ppm; 29Si-NMR: (CD3CNꢀ
/
/
/
MS (EI, 70 eV, pos.,
/
cation), 431
/
/
1
of 9 as a yellow solid. Spectroscopic data for 9: H-
NMR (CDCl3ꢀ
/
TMS): 0.53 (s, SiMe, 3H), 0.76 (s, SiMe,
3
/
3H), 2.10 (d, NMe, 3H, J(1H,1H)ꢁ
/
4.8 Hz), 2.38 (d,
NOSi: C, 58.93; H, 5.66; N, 2.64. Found: C, 58.87; H,
3
NMe, 3H, J(1H,1H)ꢁ
/4.4 Hz), 3.52 (dd, NCH2, 1H,
5.82; N, 2.73%.
2J(1H,1H)ꢁ
/
13.2 Hz), 3J(1H,1H)ꢁ
/
6.14 Hz), 4.30 (m,
NCH2), 4.22 (s, Cp, 5H), 4.33 (dd, Cp, 1H), 4.61 (t, Cp,
1H), 5.05 (dd, Cp, 1H), 7.04, 7.46 (AA?XX?, Ar-H, 2×
2H) ppm; 13C-NMR (CDCl3ꢀ
TMS): ꢃ0.92 (s, SiMe),
0.03 (s, SiMe), 39.7 (s, NMe2), 42.8 (s, NMe2), 57.0
5.4. Synthesis of derivatives of 14
/
/
/
5.4.1. Synthesis of (R,S)-FcNSiMe2C6H4CHO (18)
(method a)
ꢃ
/
(NCH2), 69.6 (Cp), 70.9 (C, Cp), 73.6 (CH, Cp), 75.5
(CH, Cp), 76.3 (CH, Cp), 78.8 (C, Cp), 115.4 (d, C2
A solution of t-BuLi (15 ml, 22.5 mmol in n-pentane)
was added slowly drop-wise to a stirred solution of 14
ortho, 2J(13C,19F)ꢁ
4J(13C,19F)ꢁ
4.0 Hz),
3J(13C,19F)ꢁ8.0 Hz), 163.8 (d, C1 ipso, J(13C,19F)ꢁ
250.1 Hz) ppm; 29Si-NMR: (CDCl3ꢀ
TMS) ꢃ8.2 (s,
SiMe2) ppm; IR (CH2Cl2): nCꢀH 3056 (w), 2990 (w)
cmꢃ1, nCꢁC 1590 (w), 1498 (w) cmꢃ1, dCꢀHꢁ
1420
(w), 1266 (s), nCꢀF
1165 (w), 1107 (s) cmꢃ1, nCꢀH
(para)ꢁ MS (EI, 70 eV, pos.,
739 (s), 705 cmꢃ1; ESꢀ
MeOH): m/eꢁ396 cation), 351
([M]ꢂ,
[FcCH2SiMe2C6H4F]ꢂ, 332 [FcCH2SiMe2C6H4]ꢂ, 199
[FcCH2]ꢂ, 826 [FcNSiMe2C6H4F× cation]ꢂ;
HClꢂ
Anal. Calc. for C21H27ClFFeNSi: C, 58.41; H, 6.30;
N, 3.24, respectively, 9×2 H2O C21H31ClFFeNO2Si: C,
/
19.2 Hz), 134.3 (d, C4 para,
(4.91 g, 11 mmol) in 50 ml THF at ꢃ
reaction mixture was stirred for 40 min at ꢃ
/
78 8C. The
/
135.7 (d, C3 meta,
/
78 8C.
1
/
/
DMF (8.51 ml, 110 mmol) was added drop-wise and
stirred for 60 min. The resulting mixture was hydrolyzed
with ammonium chloride in water at 0 8C. The liquid
layers were separated. The aqueous layer was extracted
with n-pentane, the organic layer was combined with the
extracts, and then dried over Na2SO4. Afterwards, the
solvent was removed in vacuo. A brown oil (18) was
obtained with compound 19 as impurity. The separation
of 18 from 19 was achieved by preparing the bisulfit
adduct of the aldehyde (18). The brown oil was
dissolved in diethyl ether. Then NaHSO3 was added in
/
/
ꢁ
/
ꢁ
/
/
ꢁ
/
/
/
/
/
/
/

C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ
/201
199
excess. The yellow solid was separated by filtration and
washed with hot diethyl ether. The solid was suspended
in n-pentane. Na2CO3 in water at 0 8C was added
slowly to this suspension over a period of 2 h. The
organic layers was separated and dried over Na2SO4.
The solvent was removed under reduced pressure and a
brown oil (18) was obtained. Spectroscopic data for 18:
the procedure used in method a. In method c, a solution
of n-BuLi (30.16 ml, 52.7 mmol) was added slowly drop-
wise to a stirred solution of 14 (12.02 g, 26.35 mmol) in
50 ml n-pentane at ꢃ78 8C. In this method, the phenyl
/
silane (19) and the carboxylic acid (20) were obtained as
by-products. The reaction mixture was treated with
diethyl ether. Then, the resulting yellow solid was
separated by filtration. Further purification was done
1H-NMR (CDCl3ꢀ
/
TMS): 0.57 (s, SiMe), 0.67 (s, SiMe),
2
1.92 (s, NMe2, 6H), 2.87 (d, NCH2, 1H, J(1H,1H)ꢁ
/
according to the procedure used in method a. Spectro-
1
12.44 Hz), 3.44 (d, NCH2, 1H, J(1H,1H)ꢁ
4.04 (s, br, Cp, 1H), 4.10 (s, Cp, 5H) 4.28 (t, Cp, 1H,
3J(1H,1H)ꢁ
2.2 Hz), 4.30 (s, br, Cp, 1H), 7.77, (m,
AA?XX?, Ar-H, 2×
2H), 9.99 (CHO) ppm; 13C-NMR
(CDCl3ꢀTMS): ꢃ1.7 (s, SiMe), ꢃ1.2 (s, SiMe), 44.6 (s,
/12.44 Hz),
2
scopic data for 20: H-NMR (CDCl3ꢀ
/
TMS): 0.53 (s,
SiMe), 0.76 (s, SiMe), 2.14 (s, NMe2, 6H), 3.40 (d,
2
NCH2, 1H, J(1H,1H)ꢁ
2J(1H,1H)ꢁ
13.16 Hz), 4.17 (s, Cp, 5H), 4.25 (s, br, Cp,
1H) 4.47 (s, br, Cp), 4.68 (s, br, Cp, 1H), 6.48 (COOH)
7.55, 7.98 (d, AA?XX?, Ar-H, 2× 8.0
2H, 3J(1H,1H)ꢁ
Hz), impurities Et2O:1.21, 3.49 ppm; 13C-NMR
(CDCl3ꢀTMS): ꢃ1.09 (s, SiMe), ꢃ0.33 (s, SiMe),
/
13.16 Hz), 4.01 (d, NCH2, 1H,
/
/
/
/
/
/
NMe2), 59.4 (NCH2), 68.9 (Cp), 69.0 (C, Cp), 69.9 (CH,
Cp), 74.0 (CH, Cp), 74.9 (CH, Cp), 90.4 (C, Cp), 128.2
(s, C2 ortho), 134.5 (s, C3 meta), 136.2 (s, C4 para), 149.2
/
/
/
/
/
(s, C1 ipso), 192.8 (CHO) ppm; 29Si-NMR: (CDCl3ꢀ
/
41.7 (s, NMe2), 56.5 (NCH2), 69.4 (Cp), 70.9 (C, Cp),
72.3 (CH, Cp), 74.6 (CH, Cp), 75.7 (CH, Cp), 82.5 (C,
Cp), 128.8 (s, C2 ortho), 133.5 (s, C3 meta), 136.3 (s, C4
para), 142.0 (s, C1 ipso), 172.0 (COOH), impurities
TMS)ꢃ
(w) cmꢃ1, nCꢁO
(w) cmꢃ1, nCꢀH (para)ꢁ
(EI, 70 eV, pos., THFꢀ
/
7.1 (s, SiMe2) ppm; IR (CHCl3): nCꢀH
1700 (s) cmꢃ1, nCꢁC
1591 (w), 1521
780 (s), 740 (s) cmꢃ1; ESꢀ
MS
CDCl3): m/eꢁ 1,
406 ([M]ꢂꢂ
333
ꢁ2942
/
ꢁ
/
ꢁ
/
/
/
Et2O: 15.3, 65.9; 69.2, 68.9: ppm; 29Si-NMR: (CDCl3ꢀ
TMS) ꢃ8.0 (s, SiMe2) ppm; ESꢀMS (EI, 70 eV, pos.,
MeCNꢀCH3COOH): m/eꢁ
421 ([M]ꢂ, cation), 376
[FcCH2SiMe2C6H4COOH]ꢂ,
332 [FcCH2SiMe2-
/
/
/
/
cation),
361
[FcCH2SiMe2C6H4CHO]ꢂ,
/
/
[FcCH2SiMe2C6H4]ꢂ, 199 [FcCH2]ꢂ.
/
/
C6H4]ꢂ, 299 [FcNSiMe2]ꢂ, 257 [FcCH2SiMe2]ꢂ, 199
[FcCH2]ꢂ, impurities from previous injection of 14: 457
[FcNSiMe2C6H4Br]ꢂ, 410 [FcCH2SiMe2C6H4Br]ꢂ.
5.4.2. Synthesis of (R,S)-FcNSiMe2C6H5 (19)
The compound 19 was isolated as side product during
purification of 18. Spectroscopic data for brown oil
1
(19).: H-NMR (CDCl3ꢀ/TMS): 0.56 (s, SiMe), 0.61 (s,
SiMe), 1.97 (s, NMe2, 6H), 2.96 (d, NCH2, 1H,
2J(1H,1H)ꢁ
/
12.44 Hz), 3.36 (d, NCH2, 1H,
12.44 Hz), 4.01 (s, br, Cp, 1H), 4.07 (s,
2J(1H,1H)ꢁ
/
5.4.4. Synthesis of (R,S)-FcNSiMe2C6H4CHO picrate
(21)
Compound 21 was synthesized analogously to synth-
esis of 16 with 1 g (2.47 mmol) of 18 in EtOH (25 ml).
3
Cp, 5H) 4.25 (t, Cp, 1H, J(1H,1H)ꢁ
/
2.2 Hz), 4.33 (s,
2H) ppm; 13C-
1.3 (s, SiMe), ꢃ1.0 (s, SiMe),
Cp, 1H), 7.30, 7.59 (m, AA?XX?, Ar-H, 2×
/
NMR (CDCl3ꢀTMS): ꢃ
/
/
/
The product recrystallized from hot EtOHꢀ
to yellow crystals of 21. Spectroscopic data for (21): 1H-
NMR (CDCl3ꢀTMS): 0.59 (s, SiMe, 3H), 0.84 (s, SiMe,
3H), 2.37 (s, br, NMe, 3H), 3.72 (d, NCH2, 1H,
/MeCN 1:1
44.7 (s, NMe2), 59.4 (NCH2), 68.8 (Cp), 69.8 (CH, Cp),
70.2 (C, Cp), 73.7 (CH, Cp), 74.9 (CH, Cp), 90.1 (C,
Cp), 127.4 (s, C3), 128.6 (s, C1),134.0 (s, C2), 139.9 (s,
/
C4) ppm; 29Si-NMR: (CDCl3ꢀ
7.1 (B1%) impurities of 18 ppm; ESꢀ
pos., THFꢀCDCl3): m/eꢁ
378 ([M]ꢂꢂ
[FcCH2SiMe2C6H4]ꢂ,
299
[FcNSi]ꢂ, 199 [FcCH2]ꢂ, impurities of 18: 604
/
TMS)ꢃ
/
7.8 (s, SiMe2), ꢃ
/
2J(1H,1H)ꢁ
/
13.2 Hz), 4.44 (d, NCH2, 1H,
13.2 Hz), 4.26 (s, Cp, 5H), 4.38 (s, br, Cp,
/
/
MS (EI, 70 eV,
2J(1H,1H)ꢁ
/
/
/
/
1, cation), 333
1H), 4.62 (t, Cp, 1H, J(1H,1H)ꢁ
/
5.12 Hz), 4.76 (s, Cp,
H, 3J(1H,1H)ꢁ
8.0 Hz),
H, 3J(1H,1H)ꢁ
8.0 Hz), 8.87
(s, NO2Ar-H, 2 H), 10.0 (CHO) ppm; 13C-NMR
(CD3CNꢀTMS): ꢃ1.4 (s, SiMe), ꢃ0.1 (s, SiMe), 43.0
3
[FcNSiMe2]ꢂ,
272
407
1H), 7.68 (m, AA?XX?, Ar-H, 2×
/
/
[FcNSiMe2C6H4CHOꢂ
FcCH2]ꢂ,
/
7.82 (m, AA?XX?, Ar-H, 2×
/
/
[FcNSiMe2C6H4CHO]ꢂ.
/
/
/
(br, NMe2), 59.1 (NCH2), 70.7 (Cp), 71.2 (C, Cp), 74.2
(CH, Cp), 75.7 (CH, Cp), 77.6 (CH, Cp), 81.0 (C, Cp),
129.4 (s, C2 ortho), 135.4 (s, C3 meta), 137.9 (s, C4 para),
148.4 (s, C1 ipso) 126.6, 127.3, 143.1, 162.7 (6*C,
5.4.3. Alternative syntheses of (R,S)-
FcNSiMe2C6H4CHO (18) (method b and c): synthesis
of (R,S)-FcNSiMe2C6H4COOH (20)
The synthetic procedures for preparing compound 18
according to method b and c were similar to the
procedures used in method a. In method b, a solution
of 14 (6.55 g, 14.3 mmol) in 60 ml THF with 1.00 g (41.1
mmol) magnesium was used. To this Grignard reagent a
solution of DMF (143 mmol, 11.1 ml) at 0 8C was
added slowly (1 h). Further purification was done using
NO2Ar), 193.8 (CHO) ppm; 29Si-NMR: (CDCl3ꢀ
TMS) ꢃ7.0 (s, SiMe2) ppm; ESꢀMS (EI, 70 eV, pos.,
MeCN): m/eꢁ405 1, cation), 360
([M]ꢂꢃ
/
/
/
/
/
[FcCH2SiMe2C6H4CHO]ꢂ, 198 [Fc]ꢂ; Anal. Calc. for
C28H30FeN4O8Si: C, 53.00; H, 4.76; N, 8.83. Found: C,
52.94; H, 4.91; N, 8.41%.

200
C. Beyer et al. / Journal of Organometallic Chemistry 654 (2002) 187ꢀ201
/
Table 3
Crystal data and structure refinement for solid state structures
Number
(7) FcNꢀSi(C6H4F)3
(12) FcNꢀSiMe(C6H4F)2ꢂ
(15) FcNꢀSiMe2(C6H4Br)ꢂ Clꢃ with
0.5 H2O
picrateꢃ
Empirical formula
Formula weight (g molꢃ1
Temperature (K)
C31H28F3FeNSi
555.48
293(2)
C32H30F2FeN4O7Si
704.54
293(2)
C21H27BrClFeNO0.50Si
500.74
293(2)
)
˚
Wavelength (A)
1.54178
Triclinic
Pꢃ1
1.54178
Monoclinic
C2/c
1.54178
Monoclinic
P2/c
Crystal system
Space group
Unit cell dimensions
˚
a (A)
10.440(1)
11.364(1)
13.184(2)
68.45(1)
70.28(1)
84.72(1)
1368.6(3)
2
22.061(3)
11.071(1)
27.762(3)
90
19.129(2)
7.282(1)
17.102(2)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g(8)
110.74(1)
90
107.66(1)
90
3
V (A )
˚
6341.1(11)
8
1.473
2270.0(5)
4
1.465
Z
Dcalc (gm cmꢃ3
)
1.348
5.179
Absorption coefficient (mmꢃ1
F(000)
Crystal size (mm)
)
4.744
2912
9.029
1024
576
0.3ꢄ0.2ꢄ0.15
0.3ꢄ0.25ꢄ0.2
0.3ꢄ0.3ꢄ0.15
u Range for data collection (8)
Index ranges
3.82ꢀ
/
75.05
3.40ꢀ
/
74.90
2.42ꢀ74.86
/
ꢃ135h 513, ꢃ145k 514,
ꢃ85l 516
9606
05h 527, 05k 513,
ꢃ345l 532
6692
ꢃ235h 512, ꢃ55k 59,
ꢃ205l 521
8491
Reflections collected
Independent reflections
Completeness to u (%)
Absorption correction
Max/min transmission
Refinement method
5643 [Rintꢁ0.08]
(75.058) 99.8
Empirical
6520 [Rintꢁ0.03]
(74.908) 99.6
Empirical
4666 [Rintꢁ0.08]
(74.868) 100.0
None
0.9992, 0.5225
0.9997, 0.8506
Full-matrix least-squares on F2 Full-matrix least-squares on F2
Full-matrix least-squares on F2
5643/118/325
1.016
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I ꢀ2s(I)]
R indices (all data)
6520/50/431
1.014
4666/1/247
1.023
R1ꢁ0.0605, wR2ꢁ0.1301
R1ꢁ0.1143, wR2ꢁ0.1570
R1ꢁ0.0546, wR2ꢁ0.1204
R1ꢁ0.1089, wR2ꢁ0.1419
0.353 and ꢃ0.438
R1ꢁ0.0724, wR2ꢁ0.1783
R1ꢁ0.1273, wR2ꢁ0.2167
0.943 and ꢃ1.079
Largest difference peak and hole 0.366 and ꢃ0.320
ꢃ3
˚
(e A
)
5.5. Experimental procedure for X-ray crystallography
142915 for compound 7, 142916 for compound 12,
and 169198 for compound 15. Copies of this informa-
tion may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
Diffraction measurements were done on an Enraf-
Nonius CAD-4 diffractometer using graphite-mono-
chromated Cuꢀ
/
Ka radiation with 6ꢃ
/
2u scans. The
(Fax: ꢂ44-1223-336033; e-mail: deposit@ccdc.cam.a-
c.uk or www: http://www.ccdc.cam.ac.uk).
/
structures were solved with direct methods, non-hydro-
gen atoms were located by using difference Fourier
synthesis and refined by full-matrix least-squares on F2
with anisotropic thermal parameters. Hydrogen atoms
were calculated and allowed to ride on their correspond-
ing carbon atoms. Empirical absorption corrections
were performed using psi-scans for 7 and 12. Crystal-
lographic data and the results of refinements are
summarized in Table 3.
Acknowledgements
Financial support of this work by the Deutsche
Forschungsgemeinschaft and the Fond der Chemischen
Industrie is gratefully acknowledged.
6. Supplementary material
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