Arene ruthenium metallacycles containing chelating thioamide ligands

Article abstract of DOI:10.1016/j.jorganchem.2008.12.015

Cationic, chiral arene ruthenium complexes of the type [Ru(η⁶-cym)(PPh₃){κ²N,S-PhNC(S)R}]BPh₄ were prepared in high yields by refluxing a mixture containing [(η⁶-cym)RuCl₂]₂, Ph₃P, PhNHC(S)R, NaBPh₄ and Et₃N in MeOH. A series of seven complexes with different thioamide ligands was prepared and fully characterised by spectroscopic methods including NMR spectroscopy and electrospray mass spectrometry. The solid-state structures of two complexes were determined by single crystal X-ray diffraction.

Full text of DOI:10.1016/j.jorganchem.2008.12.015

Journal of Organometallic Chemistry 694 (2009) 1283–1288
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Arene ruthenium metallacycles containing chelating thioamide ligands
*
Cansu Alagöz, David J. Brauer, Fabian Mohr
Fachbereich C – Anorganische Chemie, Bergische Universität Wuppertal, 42119 Wuppertal, Germany
a r t i c l e i n f o
a b s t r a c t
6-cym)(PPh3){
j
2N,S-PhNC(S)R}]BPh4 were
Article history:
Cationic, chiral arene ruthenium complexes of the type [Ru(
prepared in high yields by refluxing a mixture containing [(
and Et3N in MeOH. A series of seven complexes with different thioamide ligands was prepared and fully
characterised by spectroscopic methods including NMR spectroscopy and electrospray mass spectrome-
try. The solid-state structures of two complexes were determined by single crystal X-ray diffraction.
Ó 2008 Elsevier B.V. All rights reserved.
g
g
6-cym)RuCl2]2, Ph3P, PhNHC(S)R, NaBPh4
Received 16 November 2008
Received in revised form 4 December 2008
Accepted 6 December 2008
Available online 16 December 2008
Keywords:
Ruthenium
Thioamide ligands
Chelating ligands
Chiral metal complexes
X-ray structure
1. Introduction
We therefore wished to extend this chemistry by preparing
some arene ruthenium phosphine complexes containing anionic
Thioamides containing the NHC(S) unit are versatile ligands,
which upon deprotonation can coordinate to a given metal either
as monoanionic thiolato ligands or as anionic N,S-chelating ligands
via both N and S atoms forming four-membered metallacycles
(Chart 1). To the best of our knowledge, coordination as anionic
N-donors solely via the nitrogen atom has so far never been
reported.
chelating N-phenyl thioamides of the type PhNHC(S)NR2. The re-
sults of the synthesis and structural investigations of some cationic
arene ruthenium complexes containing chelating N-phenyl thio-
amide ligands are presented in this paper.
2. Results and discussion
Refluxing
PhNHC(S)R and Et3N in MeOH gave an orange solution out of
which the yellow, cationic Ru(II) complexes [Ru(
6-cym)
(PPh3){
2N,S-PhNC(S)R}]+ were isolated as their BPh4 salts in good
yields (Scheme 1).
a
mixture containing [(g
6-cym)RuCl2]2, Ph3P,
The group of Henderson has reported the synthesis and struc-
tural characterisation of various transition metal complexes con-
taining chelating thioamide derivatives including PhNHC(S)NHPh,
MeNHC(S)NHCN, Ph2NNHC(S)NHPh and PhNHC(S)NR2 [1–5]. We
have previously examined reactions, structures and anti-tumour
activity of various gold(I), platinum(II) and palladium(II) com-
plexes containing anionic S-coordinated thioamide ligands [6–9].
At present, we are also undertaking an investigation of gold(I) com-
plexes containing selenoamide ligands [10,11]. The current interest
in organometallic ruthenium complexes with anti-tumour activity
[12–16] as well as the lack of known arene ruthenium complexes
containing anionic N,S-chelating ligands prompted us to investi-
gate this class of complexes in further detail. The only reported
arene ruthenium complexes containing anionic chelating N,S-li-
g
j
These air- and moisture-stable compounds are soluble in chlo-
rinated solvents, acetone, acetonitrile and hot MeOH but insoluble
in water and Et2O. Complexes 1–7 were fully characterised by
spectroscopic methods and, in addition, the solid-state structures
of complexes 1 and 2 were determined by X-ray diffraction. The
31P{1H} NMR spectra of complexes 1–7 all show a singlet reso-
nance at ca. 40 ppm, typical for [Ru(g
6-arene)(PPh3)] type com-
plexes. The metal-centered chirality of the complexes is evident
from their 1H NMR spectra, which show doubling of the resonances
of the cymene protons (four doublets) and also the isopropyl Me-
groups (two doublets). The remaining signals from the thioamide
ligands, the PPh3 group and the BPh4 anion were unambiguously
assigned using 2-D NMR spectra (see Section 3). The deprotonation
of the thioamide ligands is confirmed by the absence of an NH sig-
nal in the 1H NMR spectra of the complexes. The positive-ion elec-
trospray mass spectra of complexes 1–7 show two signals, one
strong corresponding to the molecular ion of the cation, the other,
gands appear to be the chiral Ru(II) complex [Ru(
g
6-C6H6)(Cl)
{
j
2N,S-PhMeCHNC(S)Ph}] containing a chiral thioamide ligand
[17] and the Ru(II) complex containing an N,S-chelating triazepine
ligand (Chart 2) [18].
* Corresponding author.
E-mail address: fmohr@uni-wuppertal.de (F. Mohr).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.12.015

1284
C. Alagöz et al. / Journal of Organometallic Chemistry 694 (2009) 1283–1288
[Ru{j
2N,S-PhNC(S)NPh}2(CO)(PPh3)] [19]. The Ru–P and Ru–arene
S
distances and angles are similar to those reported for other p-cym-
ene Ru phosphine complexes [3]. The C–C bond lengths in the p-
cymene ligands of the complexes alternate in a long-short-long
pattern, which is typically observed for arenes coordinated to Ru.
The aforementioned chirality of these compounds is also observed
in the solid-state structures: Whilst crystals of complex 1 contain a
mixture of equal amounts of R and S enantiomers (an R enantiomer
is shown in Fig. 1), the crystals of complex 2 contained only the S
enantiomers. The racemic complex 2 forms separate crystals for
both the R and S enantiomers upon recrystallisation and by chance
a crystal of S enantiomer happened to have been picked for the dif-
fraction experiment.
In conclusion, we present here the synthesis, spectroscopic
properties of the first cationic arene ruthenium(II) complexes con-
taining N,S-chelating thioamide ligands which show metal-cen-
tered chirality. Further studies of this class of compounds
including their biological activity are currently in progress.
S
R1
R1
N
R2
N
R2
M
M
S
S
M
R2
N
R1
R1
N
R2
Chart 1.
3. Experimental
S
3.1. General
Me
S
N
Ru
Ru
N
Cl
Cl
1H, 13C and 31P{1H} NMR spectra were recorded on a 400 MHz
Bruker ARX spectrometer. Chemical shifts are quoted relative to
N
Ph
N
O
Me
external SiMe4 (1H, 13C) and 85% H3PO4 31P). Electrospray mass
(
Ph
Ph
spectra were measured on a Bruker MicroTOF spectrometer in po-
sitive-ion mode using solutions of the samples in MeCN. Elemental
analyses were performed by staff of the microanalytical laboratory
of the University of Wuppertal. All reactions were carried out un-
der aerobic conditions. Chemicals and solvents (HPLC grade) were
sourced commercially and used as received. The thioamides were
prepared by addition of the appropriate amines to a solution of
PhNCS in Et2O. NMR data for the two new thioamides is given be-
Chart 2.
much weaker, due to loss of the Ph3P group. The observed isotope
patterns of these signals agree well with the computed patterns for
the given formulae. The proposed structure of these compounds
was confirmed by an X-ray diffraction study of complexes 1 and
2, shown in Figs. 1 and 2, respectively. Selected bond distances
and angles are collected in Tables 1 and 2.
low. [(g
6-cym)RuCl2]2 was prepared as described in Ref. [20].
In both complexes, the cations consist of a ruthenium atom
coordinated to the deprotonated thioamide via the sulphur and
nitrogen atoms forming a four-membered metallacycle with an
S–Ru–N angle of ca. 67°. This angle is similar to that observed in
3.2. PhNHC(S)R3 tetrahydroquinoline
To a solution of 1,2,3,4-tetrahydroquinoline (thq) (1.3 mL,
0.01 mol) in Et2O (10 mL) PhNCS (1.2 mL, 0.01 mol) was added.
After stirring the mixture for 0.5 h, the colourless precipitate was
isolated by filtration, washed with pentane and dried in air. Yield:
1.73 g (64%). 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.77 (br. s, 1H,
NH), 7.11–7.45 (m, 9H, NPh, thq), 4.35 (t, J = 6.6 Hz, 2H, NCH2),
2.80 (t, J = 6.6 Hz, 2H, ArCH2), 2.07 (pent, J = 6.6 Hz,
ArCH2CH2CH2N). 13C{1H} NMR (101 MHz, CDCl3, 25 °C): d = 23.98
(ArCH2CH2), 26.67 (ArCH2), 49.28 (NCH2), 123.62 (thq), 124.42
the Ru(II) complex [Ru{
chelating N,N0-diphenylthioureido ligands [19] and also similar to
that observed in [Ru(
6-C6H6)(Cl){ 2N,S-PhMeCHNC(S)Ph}] [17].
The trigonal pyramidal coordination sphere about Ru in these com-
plexes is completed by the P-coordinated phosphine and the g6
j
2N,S-PhNC(S)NPh}2(CO)(PPh3)] containing
g
j
-
coordinated arene. Both the Ru–S and Ru–N bond distances of ca.
2.40 and 2.10 Å, respectively are similar to those observed in
H
N
R
Ph
S
BPh4
[(η6-cym)RuCl2]2
S
N
Ru
PPh3
Et3N
NaBPh4
R
Ph3P
O
N
Ph
Me
N
N
N
N
N Ph
N
N
R =
N
OEt
Ph Ph
O
Me
5
7
3
4
6
1
2
Scheme 1.

C. Alagöz et al. / Journal of Organometallic Chemistry 694 (2009) 1283–1288
1285
Fig. 1. Molecular structure of complex 1. Hydrogen atoms and the BPh4 anion have been omitted for clarity.
Fig. 2. Molecular structure of complex 2. Hydrogen atoms and the BPh4 anion have been omitted for clarity.
(o-NPh), 125.61, 126.82 (thq), 128.64 (m-NPh), 129.85, 134.92,
138.66 (thq), 139.22 (ipso-NPh), 181.19 (C@S).
(m, 4H, piperazine), 1.26 (t, J = 7.1 Hz, 3H, CH3). 13C{1H} NMR
(101 MHz, CDCl3, 25 °C): d = 14.53 (Me), 42.68 (NCH2), 61.67
(OCH2), 123.42 (o-NPh), 125.37 (p-NPh), 129.03 (m-NPh), 139.83
(ipso-NPh), 155.29 (C@O), 183.58 (C@S).
3.3. PhNHC(S)R4 ethoxycarbonylpiperazine
This was prepared as described above from 1-ethoxycarbonyl-
piperazine (1.5 mL, 0.01 mol) and PhNCS (1.2 mL, 0.01 mol). Yield:
2.89 g (98%). 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.32–7.39 (m,
2H, NPh), 7.31 (br. s, 1H, NH), 7.10–7.20 (m, 3H, NPh), 4.15 (q,
J = 7.1 Hz, 2H, OCH2), 3.78–3.89 (m, 4H, piperazine), 3.52–3.62
3.4. Preparation of [Ru(
complexes
g j
6-cym)(PPh3){ 2N,S-PhNC(S)R}]BPh4
A mixture containing [Ru(
thioamide (0.166 mmol) and Ph3 P (0.043 g, 0.164 mmol) in MeOH
g
6-cym)Cl2]2 (0.050 g, 0.082 mmol),

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C. Alagöz et al. / Journal of Organometallic Chemistry 694 (2009) 1283–1288
31P{1H} NMR (162 MHz, CDCl3, 25 °C): d = 40.54. ES-MS: m/z = 677
[M]+. Anal. Calc. for C61H60BN2PSRu (996.06): C, 73.55; H, 6.07; N,
2.81. Found: C, 73.44; H, 5.99; N, 2.75%.
Table 1
Selected bond distances [Å] and angles [deg] for complex 1.
Ru(1)–S(1)
Ru(1)–P(1)
Ru(1)–N(1)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–C(3)
Ru(1)–C(4)
Ru(1)–C(5)
2.4020(5)
2.3469(5)
2.1030(17)
2.234(2)
2.228(2)
2.243(2)
2.273(2)
2.231(2)
2.230(2)
1.7345(10)
1.743(2)
1.821(2)
67.07(5)
90.94(5)
84.841(19)
131.87(4)
129.10(4)
131.90(6)
80.70(7)
117.37(7)
107.34(7)
120.77(7)
P(1)–C(31)
P(1)–C(41)
N(1)–C(11)
N(2)–C(11)
N(1)–C(51)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
1.829(2)
1.838(2)
1.319(3)
1.341(3)
1.430(3)
1.436(3)
1.409(3)
1.423(4)
1.403(4)
1.439(3)
1.395(3)
3.6. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)R2}]BPh4 (2)
Yield: 0.114 g (68%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.35–7.56 (m, 23H, Ph3Ph, o-BPh4), 7.27 (t, J = 7.6 Hz,
2H, m-NPh), 7.13 (t, J = 7.1, 1.0 Hz, 1H, p-NPh), 7.00 (t, J = 7.1 Hz,
8H, m-BPh4), 6.85 (t, J = 7.1 Hz, 4H, p-BPh4), 6.70 (d, J = 7.1 Hz,
2H, o-NPh), 5.34 (d, J = 5.6 Hz, 1H, cym), 4.80 (d, J = 6.1 Hz, 1H,
cym), 4.72 (d, J = 6.1 Hz, 1H, cym), 4.64 (d, J = 5.6 Hz, 1H, cym),
2.63 (br. s, 4H, NCH2), 2.26 (sept, J = 6.6 Hz, 1H, Me2CH), 1.59 (br.
s, 2H, CH2), 1.41 (br. s, 2H, CH2), 1.32 (s, 3H, Me), 1.19 (d,
J = 7.1 Hz, 3H, Me2CH), 1.05 (d, J = 7.1 Hz, 3H, Me2CH). 31P{1H}
NMR (162 MHz, CDCl3, 25 °C): d = 40.00. ES-MS: m/z = 703 [M]+,
441 [MꢀPPh3]+. Anal. Calc. for C63H62BN2PSRu (1022.10): C,
74.03; H, 6.11; N, 2.74. Found: C, 73.64; H, 6.23; N, 2.66%.
Ru(1)–C(6)
Cga–Ru(1)
S(1)–C(11)
P(1)–C(21)
S(1)–Ru(1)–N(1)
P(1)–Ru(1)–N(1)
S(1)–Ru(1)–P(1)
Cg–Ru(1)–S(1)
Cg–Ru(1)–P(1)
Cg–Ru(1)–N(1)
C(11)–S(1)–Ru(1)
C(21)–P(1)–Ru(1)
C(31)–P(1)–Ru(1)
C(41)–P(1)–Ru(1)
C(21)–P(1)–C(31)
C(21)–P(1)–C(41)
C(31)–P(1)–C(41)
C(11)–N(1)–C(51)
C(11)–N(1)–Ru(1)
C(51)–N(1)–Ru(1)
N(1)–C(11)–N(2)
N(1)–C(11)–S(1)
N(2)–C(11)–S(1)
105.97(10)
98.52(9)
105.49(10)
124.35(17)
103.48(13)
126.64(13)
128.81(19)
108.73(15)
122.42(17)
3.7. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)R3}]BPh4 (3)
a
Cg is the centroid defined by the ring atoms C(1)–C(6).
Yield: 0.109 g (62%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.36–7.51 (m, 23H, Ph3Ph, o-BPh4), 7.06 (t, J = 7.6 Hz,
2H, m-NPh), 7.00 (t, J = 7.1 Hz, 8H, m-BPh4), 6.95 (m, 1H, thq),
6.87 (m, 5H, p-BPh4, thq), 6.77 (t, J = 7.6 Hz, 1H, p-NPh), 6.53 (m,
3H, o-NPh, thq), 5.66 (m, 1H, thq), 5.32 (d, J = 6.6 Hz, 1H, cym),
5.14 (d, J = 6.1 Hz, 1H, cym), 4.84 (d, J = 6.6 Hz, 1H, cym), 4.61 (d,
J = 6.1 Hz, 1H, cym), 3.26 (m, 1H, thq), 2.98 (m, 1H, thq), 2.48 (m,
1H, thq), 2.33 (sept, J = 7.1 Hz, 1H, Me2CH), 1.76 (m, 1H, thq),
1.63 (m, 1H, thq), 1.25 (s, 3H, Me), 1.18 (d, J = 7.1 Hz, 3H, Me2CH),
1.12 (d, J = 7.1 Hz, 3H, Me2CH). 31P{1H} NMR (162 MHz, CDCl3,
25 °C): d = 40.73. ES-MS: m/z = 765 [M]+ 503 [MꢀPPh3]+. Anal. Calc.
for C68H64BN2PSRu ꢁ H2O (1102.19): C, 74.10; H, 6.04; N, 2.54.
Found: C, 74.44; H, 6.23; N, 2.58%.
Table 2
Selected bond distances [Å] and angles [deg] for complex 2.
Ru(1)–S(1)
Ru(1)–P(1)
Ru(1)–N(1)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–C(3)
Ru(1)–C(4)
Ru(1)–C(5)
2.4020(9)
2.3602(8)
2.088(3)
2.293(4)
2.193(4)
2.215(4)
2.253(3)
2.234(3)
2.236(4)
P(1)–C(51)
P(1)–C(41)
N(1)–C(11)
N(2)–C(11)
N(1)–C(31)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
1.825(3)
1.832(4)
1.316(5)
1.345(5)
1.437(4)
1.407(5)
1.432(5)
1.409(6)
1.428(6)
1.412(6)
1.420(6)
Ru(1)–C(6)
Ru(1)–Cga
1.7317(14)
1.742(3)
S(1)–C(11)
3.8. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)R4}]BPh4 (4)
P(1)–C(61)
1.823(3)
S(1)–Ru(1)–N(1)
P(1)–Ru(1)–N(1)
S(1)–Ru(1)–P(1)
Cg–Ru(1)–S(1)
Cg–Ru(1)–P(1)
Cg–Ru(1)–N(1)
C(11)–S(1)–Ru(1)
C(61)–P(1)–Ru(1)
C(51)–P(1)–Ru(1)
C(41)–P(1)–Ru(1)
67.33(8)
90.11(8)
85.91(3)
128.80(6)
131.00(6)
131.86(10)
80.10(12)
107.16(10)
120.97(12)
118.62(11)
C(61)–P(1)–C(51)
C(61)–P(1)–C(41)
C(51)–P(1)–C(41)
C(11)–N(1)–C(31)
C(11)–N(1)–Ru(1)
C(31)–N(1)–Ru(1)
N(1)–C(11)–N(2)
N(1)–C(11)–S(1)
N(2)–C(11)–S(1)
103.40(16)
107.22(17)
97.89(15)
126.0(3)
103.4(2)
126.4(2)
128.3(3)
109.1(2)
122.6(3)
Yield: 0.152 g (84%) yellow solid. 1H NMR (400 MHz, acetone-
d6, 25 °C): d = 7.51–7.64 (m, 15H, Ph3P), 7.40 (t, J = 7.6 Hz, 2H, m-
NPh), 7.31–7.37 (m, 8H, o-BPh4), 7.21 (t, J = 7.6 Hz, 1H, p-NPh),
7.08 (d, J = 7.6 Hz, 2H, o-NPh), 6.92 (t, J = 7.1 Hz, 8H, m-BPh4),
6.77 (t, J = 7.1 Hz, 4H, p-BPh4), 5.81 (d, J = 6.1 Hz, 1H, cym), 5.49
(d, J = 5.6 Hz, 1H, cym), 5.35 (d, J = 5.6 Hz, 1H, cym), 5.21 (d,
J = 6.1 Hz, 1H, cym), 4.02 (q, J = 7.1 Hz, 2H, OCH2), 3.06–3.23 (m,
4H, piperazine), 2.81 (t, J = 5.6 Hz, 4H, piperazine), 2.50 (sept,
J = 6.6 Hz, 1H, Me2CH), 1.56 (s, 3H, Me), 1.26 (d, J = 6.6 Hz, 3H,
Me2CH), 1.14–1.19 (m, 3H, Me2CH, CH3CH2). 31P{1H} NMR
(162 MHz, acetone-d6, 25 °C): d = 40.37. ES-MS: m/z = 790 [M]+,
528 [MꢀPPh3]+. Anal. Calc. for C66H67BN3O2PSRu (1109.18): C,
71.47; H, 6.09; N, 3.79. Found: C, 71.49; H, 6.27; N, 3.43%.
a
Cg is the centroid defined by the ring atoms C(1)–C(6).
(15 mL) and Et3N (1 mL) was heated to reflux for ca. 5 min. To the
hot solution was added solid NaBPh4 (0.058 g, 0.169 mmol), which
caused precipitation of a yellow solid on cooling. The product was
isolated by filtration, washed with H2O, a little cold MeOH, Et2O
and was subsequently dried in vacuum.
3.9. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)NR5}]BPh4 (5)
Yield: 0.154 g (91%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.35–7.55 (m, 23H, Ph3Ph, o-BPh4), 7.29 (t, J = 7.6 Hz,
2H, m-NPh), 7.16 (t, J = 7.6, 1.0 Hz, 1H, p-NPh), 7.00 (t, J = 7.1 Hz,
8H, m-BPh4), 6.86 (t, J = 7.1 Hz, 4H, p-BPh4), 6.74 (d, J = 7.6 Hz,
2H, o-NPh), 5.23 (d, J = 6.1 Hz, 1H, cym), 4.77 (d, J = 6.1 Hz, 1H,
cym), 4.72 (d, J = 5.6 Hz, 1H, cym), 4.61 (d, J = 5.6 Hz, 1H, cym),
3.28 (m, 4H, CH2O), 2.68 (m, 4H, NCH2), 2.26 (sept, J = 6.6 Hz, 1H,
Me2CH), 1.27 (s, 3H, Me), 1.19 (d, J = 6.6 Hz, 3H, Me2CH), 1.05 (d,
J = 6.6 Hz, 3H, Me2CH). 31P{1H} NMR (162 MHz, CDCl3, 25 °C):
d = 39.89. ES-MS: m/z = 719 [M]+. Anal. Calc. for C63H62BN2OPSRu
(1038.10): C, 72.89; H, 6.02; N, 2.70. Found: C, 72.83; H, 6.12; N,
2.43%.
Using this procedure the following compounds were prepared.
3.5. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)NMe2}]BPh4 (1)
Yield: 0.141 g (87%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.33–7.54 (m, 23H, Ph3Ph, o-BPh4), 7.28 (t, J = 8.1 Hz,
2H, m-NPh), 7.12 (dt, J = 7.6, 1.0 Hz, 1H, p-NPh), 6.99 (t, J = 7.6 Hz,
8H, m-BPh4), 6.85 (t, J = 7.1 Hz, 4H, p-BPh4), 6.71 (d, J = 8.6 Hz,
2H, o-NPh), 5.27 (d, J = 6.6 Hz, 1H, cym), 4.87 (d, J = 5.6 Hz, 1H,
cym), 4.77 (d, J = 6.6 Hz, 1H, cym), 4.67 (d, J = 6.1 Hz, 1H, cym),
2.25 (sept, J = 7.1 Hz, 1H, Me2CH), 2.15 (s, 6H, NMe2), 1.31 (s, 3H,
Me), 1.17 (d, J = 6.6 Hz, 3H, Me2CH), 1.07 (d, J = 6.6 Hz, 3H, Me2CH).

C. Alagöz et al. / Journal of Organometallic Chemistry 694 (2009) 1283–1288
1287
3.10. [Ru(
g
6-cym)(PPh3){
j
2N,S-PhNC(S)NR6}]BPh4 (6)
3.12. X-ray crystallography
Yield: 0.081 g (44%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.33–7.54 (m, 23H, Ph3Ph, o-BPh4), 7.24 (m, 6H, m-
NPh, Bz), 7.08 (m, 3H, p-NPh, Bz), 7.00 (t, J = 7.1 Hz, 8H, m-BPh4),
6.80–6.91 (m, 8H, p-BPh4, Bz), 6.48 (d, J = 7.6 Hz, 2H, o-NPh), 5.33
(d, J = 6.1 Hz, 1H, cym), 4.86 (d, J = 6.1 Hz, 1H, cym), 4.69 (d,
J = 6.6 Hz, 1H, cym), 4.60 (d, J = 6.6 Hz, 1H, cym), 3.97 (AB quart,
J = 15.8 Hz, 4H, NCH2), 2.29 (sept, J = 7.1 Hz, 1H, Me2CH), 1.26 (s,
3H, Me), 1.20 (d, J = 7.1 Hz, 3H, Me2CH), 1.03 (d, J = 7.1 Hz, 3H,
Me2CH). 31P{1H} NMR (162 MHz, CDCl3, 25 °C): d = 36.86. ES-MS:
m/z = 829 [M]+, 567 [MꢀPPh3]+. Anal. Calc. for C73H68BN2PSRu
(1148.25): C, 76.36; H, 6.07; N, 5.97. Found: C, 76.64; H, 6.36; N,
5.77%.
Crystals of complexes 1 and 2 suitable for X-ray diffraction were
obtained by slow diffusion of ether into a CH2Cl2 solution of the
compound. The crystals were fastened with epoxy glue to glass fi-
bres. After cooling the crystals to ꢀ100 °C with a Siemens LT-2A
device, data were measured using a Bruker P4-SMART diffractom-
eter employing graphite monochromatised Mo
K
a
radiation
(k = 0.71073 Å). For each compound a series of u and
x
scans were
used to generate 1650 CCD frames from which the reflections were
harvested and the cell constants in Table 1 were determined. The
intensities were corrected by integration for absorption and scaled.
Direct methods (SHELXS) [21] yielded the positions of most of the
non-hydrogen atoms, and the structures were completed with
standard difference Fourier techniques. While the locations of
hydrogen atoms were apparent from the
DF maps, these atoms
3.11. [Ru(g j
6-cym)(PPh3){ 2N,S-PhNC(S)R6}]BPh4 (7)
were idealized and their parameters were constrained during
refinement. Initial refinement of complex 2 gave unusually large
thermal parameters for the C(23) atom of the pyrrolidino group
Yield: 0.113 g (63%) yellow solid. 1H NMR (400 MHz, CDCl3,
25 °C): d = 7.36–7.56 (m, 23H, Ph3Ph, o-BPh4), 7.30 (t, J = 7.6 Hz,
2H, m-NPh), 7.22 (t, J = 7.6 Hz, 2H, pipNPh), 7.17 (t, J = 7.6,
1.0 Hz, 1H, p-NPh), 6.99 (t, J = 7.6 Hz, 8H, m-BPh4), 6.82–6.90
(m, 5H, p-BPh4, pipNPh), 6.71–6.79 (m, 4H, o-NPh, pipNPh), 5.34
(d, J = 6.6 Hz, 1H, cym), 4.78 (d, J = 5.6 Hz, 1H, cym), 4.74 (d,
J = 6.6 Hz, 1H, cym), 4.62 (d, J = 5.6 Hz, 1H, cym), 2.76–2.89 (m,
8H, pip), 2.28 (sept, J = 7.1 Hz, 1H, Me2CH), 1.27 (s, 3H, Me),
1.19 (d, J = 7.1 Hz, 3H, Me2CH), 1.06 (d, J = 7.1 Hz, 3H, Me2CH).
31P{1H} NMR (162 MHz, CDCl3, 25 °C): d = 39.86. ES-MS: m/
z = 794 [M]+, 532 [MꢀPPh3]+. Anal. Calc. for C69H67BN3PSRu
(1113.21): C, 74.45; H, 6.07; N, 3.77. Found: C, 74.15; H, 6.02;
N, 3.67%.
and a
DF synthesis showed that this atom was disordered over
two sites. Presumably the pyrrolidino ring adopts an envelope con-
formation with the flap atom C(23) occurring alternatively above
and below the plane of the other four ring atoms. Accordingly,
the C(23) atom was split and appropriate constraints of ring geom-
etry and positions of the idealized hydrogen atoms were applied in
the least-squares process. This model converged with the flap atom
essentially evenly divided [occupancies 0.48(3) and 0.52(3)] on the
two sides of the ring. Important crystallographic and refinement
details are listed in Table 3. SHELXL, and PLATON were used for the data
refinement and additional geometrical calculations [21,22].
Acknowledgements
F.M. gratefully acknowledges generous support from the Fonds
der Chemischen Industrie as well as the University of Wuppertal
for this project.
Table 3
Crystallographic and refinement data for complexes 1 and 2.
Empirical
formula
C61H60BN2PRuS
C64H63BCl3N2PRuS
Formula weight 996.02
1141.42
Monoclinic
P21
10.4223(5)
25.3367(13)
10.8180(5)
90
104.3471(6)
90
2767.6(4)
2
1.370
1.94–29.91
Appendix A. Supplementary material
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
P1
ꢀ
CCDC 709684 and 709685 contain the supplementary crystallo-
graphic data for 1 and 2. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif. Supplementary data associated with
this article can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.12.015.
11.3402(4)
11.6669(4)
20.1877(7)
75.6634(5)
79.6546(5)
80.1345(6)
2523.0(3)
2
a
(°)
b (°)
c
(°)
0
V (ÅA3)
Z
Dcalc. (g cmꢀ3
)
1.311
References
H
range (°)
1.84–29.88
Limiting indices ꢀ15 6 h 6 11, ꢀ10 6 k 6 15,
ꢀ13 6 h 6 14, ꢀ35 6 k 6 34,
[1] W. Henderson, B.K. Nicholson, Polyhedron 15 (1996) 4015.
[2] W. Henderson, B.K. Nicholson, C.E.F. Rickard, Inorg. Chim. Acta 320 (2001) 101.
[3] W. Henderson, B.K. Nicholson, M.B. Dinger, R.L. Bennett, Inorg. Chim. Acta 338
(2002) 210.
[4] W. Henderson, C.E.F. Rickard, Inorg. Chim. Acta 343 (2003) 74.
[5] W. Henderson, B.K. Nicholson, E.R.T. Tiekink, Inorg. Chim. Acta 359 (2006) 204.
[6] E. Vergara, S. Miranda, F. Mohr, E. Cerrada, E.R.T. Tiekink, P. Romero, M. Laguna,
Eur. J. Inorg. Chem. (2007) 2926.
[7] S. Miranda, E. Vergara, F. Mohr, D. de Vos, E. Cerrada, A. Mendía, M. Laguna,
Inorg. Chem. 47 (2008) 5641.
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Tiekink, F. Mohr, J. Inorg. Biochem. 102 (2008) 2067.
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146.
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1050.
[11] A. Molter, D. Gallenkamp, T. Porsch, F. Mohr, unpublished results.
[12] I. Bratsos, S. Jedner, T. Gianferrara, E. Alessio, Chimia 61 (2007) 692.
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4764.
[14] M. Gielen, E.R.T. Tiekink, Metallotherapeutic Drugs & Metal-based Diagnostic
Agents, John Wiley & Sons, Chichester, 2005.
ꢀ27 6 l 6 28
ꢀ14 6 l 6 4
Reflections
collected
Unique
19708
21381
12862
0.0401
11217
14011
0.0510
12696
[R(int)
Observed
[I > 2
]
r
(I)]
Crystal size
0.68 ꢂ 0.34 ꢂ 0.10
0.52 ꢂ 0.20 ꢂ 0.10
(mm)
l
(mmꢀ1
)
0.425
0.537
0.95579–0.79244
0.0549
0.1276
1.056
Transmission
R1 (all data)
wR2 (all data)
0.95864–0.85136
0.0534
0.1359
Goodness-of-fit 1.079
on F2
Parameters 0
F map (e ÅAꢀ3
Flack
parameter
609
671
D
)
1.101 to ꢀ1.654
1.176 to ꢀ1.393
–
ꢀ0.04(2)

1288
C. Alagöz et al. / Journal of Organometallic Chemistry 694 (2009) 1283–1288
[15] C.S. Allardyce, A. Dorcier, C. Scolaro, P.J. Dyson, Appl. Organomet. Chem. 19
(2005) 1.
[16] M.J. Clarke, Coord. Chem. Rev. 236 (2003) 209.
[17] H. Brunner, T. Zwack, M. Zabel, Z. Kristallogr. 217 (2002) 551.
[18] M. Aitali, M.Y. Ait Itto, A. Hasnaoui, A. Riahi, A. Karim, J.C. Daran, J. Organomet.
Chem. 619 (2001) 265.
[19] S.D. Robinson, A. Sahajpal, J.W. Steed, Inorg. Chim. Acta 306 (2000) 205.
[20] M.A. Bennett, A.K. Smith, J. Chem. Soc., Dalton Trans. (1974) 233.
[21] G.M. Sheldrick, SHELXTL-NT 6.1, Universität Göttingen, 1998.
[22] A.L. Spek, Acta Crystallogr. A 46 (1990) C34.