Synthesis of oxo- and sulfido-bridged germanium-ruthenium complexes and reactions on the chalcogenido bridges

Article abstract of DOI:10.1021/om060449m

A series of heterodinuclear germanium-ruthenium complexes having sulfido/oxo bridges, Dmp(Dep)-Ge(μ-E¹)(μ-E²) Ru(η⁶-arene) (E¹, E² = S, O; arene -benzene, p-cymene; Dmp = 2,6-dimesitylphenyl, Dep = 2,

Full text of DOI:10.1021/om060449m

Organometallics 2006, 25, 4835-4845
4835
Synthesis of Oxo- and Sulfido-Bridged Germanium-Ruthenium
Complexes and Reactions on the Chalcogenido Bridges
Tsuyoshi Matsumoto, Yukiko Nakaya, and Kazuyuki Tatsumi*
Department of Chemistry, Graduate School of Science, Research Center for Materials Science, Nagoya
UniVersity, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan
ReceiVed May 23, 2006
A series of heterodinuclear germanium-ruthenium complexes having sulfido/oxo bridges, Dmp(Dep)-
Ge(µ-E1)(µ-E2)Ru(η6-arene) (E1, E2 ) S, O; arene ) benzene, p-cymene; Dmp ) 2,6-dimesitylphenyl,
Dep ) 2,6-diethylphenyl) were synthesized by the reaction of [Ru(η6-arene)Cl2]2 and the corresponding
diarylgermanedichalcogenoles, Dmp(Dep)Ge(E1H)(E2H). The reaction with tertiary phosphines gave the
corresponding adducts Dmp(Dep)Ge(µ-S)(µ-E)Ru(PR3) (E ) S, O; R ) Ph, Et), in which the arene
ligand on the ruthenium was replaced by a mesityl group of Dmp. When Dmp(Dep)Ge(µ-S)2Ru(PPh3)
was treated with the Brønsted acids H(OEt2)2BArF4 and HOTf, a sulfido bridge was protonated to afford
[Dmp(Dep)Ge(µ-S)(µ-SH)Ru(PPh3)]X (X ) BArF , OTf). Likewise, the methylation reaction with
4
Me3OBF4 proceeded at a µ-S, generating [Dmp(Dep)Ge(µ-S)(µ-SMe)Ru(PPh3)](BF4). On the other hand,
protonation of Dmp(Dep)Ge(µ-S)(µ-O)Ru(PPh3) gave a µ-OH complex, [Dmp(Dep)Ge(µ-S)(µ-OH)Ru-
(PPh3)]+, while the analogous methylation afforded the cationic µ-SMe complex [Dmp(Dep)Ge(µ-SMe)-
(µ-O)Ru(PPh3)]+.
closely related thiolate/alkoxide series.8,9 We report herein a
new series of bis(chalcogenido)-bridged heterodinuclear com-
plexes containing germanium, a main-group element, and
ruthenium, a late transition metal. These complexes are of
interest from the following points of view. First, heterodinuclear
germanium-ruthenium complexes that have three different types
of bis(chalcogenido) bridges, bis(µ-sulfido), µ-sulfido/µ-oxo, and
bis(µ-oxo) complexes, allow a systematic comparison of their
structures and the reactions of thiolates and alkoxides. These
complexes were prepared using Dmp(Dep)Ge(SH)2,10,11 Dmp-
(Dep)Ge(SH)(OH), and Dmp(Dep)Ge(OH)2, respectively, which
were readily prepared in a few steps by sulfurization or oxidation
of Dmp(Dep)GeH2 (Dmp ) 2,6-dimesitylphenyl, Dep ) 2,6-
diethylphenyl). Another interesting point with regard to the
heterodinuclear Ge-Ru system arises from the possible coop-
erativity of Ge and Ru in reactions. The semimetallic nature of
the heavy group 14 element could confer intriguing reactivities
to the transition-metal chalcogenides. Metallacycles that consist
of chalcogens, late transition metals, and heavy group 14
elements are scarce. In fact, there have been no reports of the
metallacycles that contain an S/O mixed system. Ando et al.
Introduction
Transition-metal thiolato complexes have been widely studied
due to their structural diversity and versatile reactivities, which
may be related to unique functions of sulfur-containing active
sites of metalloenzymes.1 The chemistry of alkoxido complexes
of transition metals also is quite varied, and its importance has
been manifested in its broad application to various organo-
metallic reactions.2 However, research that sheds light on the
differences between late-transition-metal sulfides and oxides is
limited. A few reports have focused on the relative stabilities
of thiolates and alkoxides of late-transition-metal complexes.3-7
Although the reactions of thiolato sulfurs and alkoxido oxygens
coordinated to late transition metals have also been investigated
by alkylation, protonation, metalation, and so forth, their
differences have not been understood clearly due to the lack of
(1) (a) Transition Metal Sulfur Chemistry, Biological and Industrial
Significance; Steifel, E. I., Matsumoto, K., Eds,; American Chemical
Society: Washington, DC, 1996. (b) Transition Metal Sulphides-Chemistry
and Catalysis; Weber, Th., Prons, R., van Santen, R. A., Eds.; Kluwer
Academic: Dordrecht, The Netherlands, 1998.
(2) (a) Bradley, D. C.; Mehrotra, R. C.; Rothwell, I. P.; Singh, A. Alkoxo
and Aryloxo DeriVatiVes of Metals; Academic Press: San Diego, CA, 2001.
(b) Fulton, J. R.; Holland, A. W.; Fox, D. J.; Bergman, R. G. Acc. Chem.
Res. 2002, 35, 44. (c) Bryndza, H. E.; Tam, W. Chem. ReV. 1988, 88, 1163.
(3) (a) Burn, M. J.; Fickes, M. G.; Hollander, F. J.; Bergman, R. G.
Organometallics 1995, 14, 137. (b) Michelman, R. I.; Ball, G. E.; Bergman,
R. G.; Andersen, R. A. Organometallics 1994, 13, 869. (c) Hartwig, J. F.;
Anderson, R. A.; Bergman, R. G. Organometallics 1991, 10, 1875.
(4) Li, H.-C.; Nolan, S. P.; Peterson, J. L. Organometallics 1998, 17,
3516.
(5) Milstein, D.; Calabrese, J. C.; Williams, I. D. J. Am. Chem. Soc.
1986, 108, 6387.
(6) (a) Ko¨lle, U.; Rietmann, C.; Englert, U. J. Organomet. Chem. 1992,
423, C20. (b) Ho¨rnig, A.; Rietmann, C.; Englert, U.; Wagner, T.; Ko¨lle, U.
Chem. Ber. 1993, 126, 2609.
(8) For some recent examples, see: (a) McGuire, D. G.; Kahn, M. A.;
Ashby, M. T. Inorg. Chem. 2002, 41, 2202. (b) Grapperhaus, C. A.;
Poturovic, S.; Mashuta, M. S. Inorg. Chem. 2002, 41, 4309. (c) Shin, R. Y.
C.; Bennett, M. A.; Goh, L. Y.; Chen, W.; Hockless, D. C. R.; Leong, W.
K.; Mashima, K.; Willis, A. C. Inorg. Chem. 2003, 42, 96. (d) Sellmann,
D.; Weber, M.; Binder, H.; Boese, R. Z. Naturforsch., B: Chem. Sci. 1986,
41b, 1541. (e) Grapperhaus, C. A.; Darensbourg, M. Y. Acc. Chem. Res.
1998, 31, 451.
(9) (a) Desiraju, G. R.; Steiner, T. The Weak Hydrogen Bond, In
Structural Chemistry and Biology; Oxford University Press: Oxford, U.K.,
1999. (b) Miyaki, Y.; Onishi, T.; Kurosawa, H. Inorg. Chim. Acta 2000,
300-302, 369. (c) Ohnishi, T.; Miyaki, Y.; Asano, H.; Kurosawa, H. Chem.
Lett. 1999, 809. See also ref 2.
(10) (a) Matsumoto, T.; Tatsumi, K. Chem. Lett. 2001, 964. (b)
Matsumoto, T.; Matsui, Y.; Nakaya, Y.; Tatsumi, K. Chem. Lett. 2001, 60.
(11) (a) Matsumoto, T.; Tokitoh, N.; Okazaki, R. J. Am. Chem. Soc.
1999, 121, 8811. (b) Tokitoh, N.; Matsumoto, T.; Okazaki, R. Bull. Chem.
Soc. Jpn. 1999, 72, 1665.
(7) (a) Fox, P. A.; Bruck, M. A.; Gray, S. D.; Gruhn, N. E.; Grittini, C.;
Wigley, D. E. Organometallics 1998, 17, 2720. (b) Chisholm, M. H.;
Davidson, E. R.; Huffman, J. C.; Quinlan, K. B. J. Am. Chem. Soc. 2001,
123, 9652.
10.1021/om060449m CCC: $33.50 © 2006 American Chemical Society
Publication on Web 08/31/2006

4836 Organometallics, Vol. 25, No. 20, 2006
Matsumoto et al.
Scheme 1
Figure 1. Molecular structure of Dmp(Dep)Ge(µ-S)2Ru(η6-p-
cymene) (1a) with thermal ellipsoids drawn at the 40% level.
and Steudel et al. reported independently on four- and five-
membered dithiatitana- and dithiazirconacycles containing
silicon, germanium, and tin.12 Recently, Holl et al. reported the
synthesis of dinuclear germanium-platinum and germanium-
palladium complexes containing oxo or sulfido bridges in the
course of their studies of germylene complexes.13 Thiolato-
bridged heterodinuclear Ru-M (M ) Ge, Sn, Pb) complexes
were also synthesized by Goh via the reaction of the ruthenium
thiolate [(η6-C6Me6)Ru(tpdt)] (tpdt ) 3-thiapentane-1,5-dithio-
late) with Ph3MCl.14
complex, exhibiting two singlets for the four mesityl aromatic
protons and two singlets for the four o-Me group protons. Two
m-CH protons of the Dmp central ring are also inequivalent.
The UV-vis spectra of 1a,b-3a,b each show an absorption
band characteristic of coordinatively unsaturated half-sandwich
ruthenium complexes. Complexes 1a,b show bands at 658 and
660 nm, respectively, which are similar to those of (η6-arene)-
Ru(SR)2 and related coordinatively unsaturated complexes.15
The bands are blue-shifted on going from the complexes with
bis(sulfido) bridges to sulfido/oxo bridges and to bis(oxo)
bridges, where the corresponding bands for 2a,b and 3a,b appear
at 598, 601 nm and 475, 476 nm, respectively. As is evident
from the large ꢀ values (∼103) and from the observed blue shift,
the absorptions are attributable to the LMCT transitions from
the pπ orbitals of the bridging chalcogens to a vacant Ru d
orbital. A similar hypsochromic shift was reported for the
absorption band of (η6-arene)Ru(SAr)2 relative to that of the
selenolato analogue.15c
Crystal Structures of 1a-3a. The monomeric nature of
complexes 1a-3a was confirmed by X-ray structural analysis.
The molecular structure of 1a is shown in Figure 1, while the
structures of the other compounds are very much alike; selected
bond distances and angles are given in Table 1. The bulky aryl
groups on Ge and η6-arene on Ru prevent the molecule from
being dimerized. The geometry around the ruthenium may be
described as a two-legged piano stool. All of the four-membered
Ge(µ-E1)(µ-E2)Ru rings are approximately planar, and the largest
deviation from planarity was found for 1a, in which the dihedral
angle between the planes S(1)-Ge(1)-S(2) and S(1)-Ru(1)-
S(2) is 11.6°. The planar geometry would enhance the π overlap
between S (or O) pπ orbitals and a vacant Ru d orbital to ease
the electron deficiency at Ru, as was discussed for Cp*Ru-
(PR3)X by Caulton et al.16 The multiple-bonding character of
Results and Discussion
Synthesis of Dmp(Dep)Ge(µ-E1)(µ-E2)Ru(η6-arene) (E1, E2
) O, S). Bis(µ-sulfido) Ge-Ru complexes, Dmp(Dep)Ge(µ-
S)2Ru(η6-arene) (arene ) p-cymene (1a), arene ) benzene (1b)),
were isolated as deep blue crystals in 87 and 84% yields,
respectively, from the reactions of the corresponding [(η6-arene)-
RuCl2]2 complexes and Dmp(Dep)Ge(SLi)2, which was prepared
from Dmp(Dep)Ge(SH)2 and 2 equiv of n-BuLi in THF (Scheme
1).10 All of the spectral data are in accord with the above
1
formulation. In the H NMR spectra, the aromatic protons of
the η6-coordinated p-cymene of 1a were observed at δ 4.71
and 4.57 as an AX pattern. The η6-benzene proton signal of 1b
was observed as a singlet at δ 4.74. Despite the coordinative
unsaturation of the ruthenium, these complexes are quite stable
in air, even in a toluene solution.
Similarly, the µ-oxo/µ-sulfido and the bis(µ-oxo) complexes
Dmp(Dep)Ge(µ-S)(µ-O)Ru(η6-arene) (arene ) p-cymene (2a),
benzene (2b)) and Dmp(Dep)Ge(µ-O)2Ru(η6-arene) (arene )
p-cymene (3a), benzene (3b)) were synthesized from Dmp-
(Dep)Ge(SH)(OH) and Dmp(Dep)Ge(OH)2, respectively, as
deep purple and reddish purple crystals. Because a mixture of
R and S isomers of Dmp(Dep)Ge(SH)(OH) was used for the
reactions, 2a,b were obtained as racemic mixtures. The chirality
at Ge is reflected by the 1H NMR spectra of 2a,b. For instance,
two mesityl groups of Dmp are observed independently in each
(15) (a) Mashima, K.; Mikami, A.; Nakamura, A. Chem. Lett. 1992, 1473.
(b) Mashima, K.; Kaneyoshi, H.; Kaneko, S.; Mikami, A.; Tani, K.;
Nakamura, A. Organometallics 1997, 16, 1016. (c) Mashima, K.; Kaneko,
S.; Tani, K.; Kaneyoshi, H.; Nakamura, A. J. Organomet. Chem. 1997,
545-546, 345. (d) Herberhold, M.; Yan, H.; Milius, W. J. Organomet.
Chem. 2000, 598, 142. (e) Won, J.-H.; Lim, H.-G.; Kim, B. Y.; Lee, J.-D.;
Lee, C.; Lee, Y.-J.; Cho, S.; Ko, J.; Kang, S. O. Organometallics 2002, 21,
5703.
(16) (a) Johnson, T. J.; Folting, K.; Streib, W. E.; Martin, J. D.; Huffman,
J. C.; Jackson, S. A.; Einstein, O.; Caulton, K. D. Inorg. Chem. 1995, 34,
488. (b) Lunder, D. M.; Lobkovsky, E. B.; Streib, W. E.; Caulton, K. G. J.
Am. Chem. Soc. 1991, 113, 1837.
(12) (a) Choi, N.; Sugi, S.; Ando, W. Chem. Lett. 1994, 1395. (b) Choi,
N.; Morino, S.; Sugi, S.; Ando, W. Bull. Chem. Soc. Jpn. 1996, 69, 1613.
(c) Albertsen, J.; Steudel, R. J. Organomet. Chem. 1992, 424, 153.
(13) (a) Cygan, Z. T.; Bender, J. E., IV; Litz, K. E.; Kampf, J. W.; Holl,
M. M. B. Organometallics 2002, 21, 5373. (b) Cygan, Z.; Kampf, J. W.;
Holl, M. M. B. Inorg. Chem. 2003, 42, 7219.
(14) Shin, R. Y. C.; Vittal, J. J.; Zhou, Z.-Y.; Koh, L. L.; Goh, L. Y.
Inorg. Chim. Acta 2003, 352, 220.

Oxo- and Sulfido-Bridged Ge-Ru Complexes
Organometallics, Vol. 25, No. 20, 2006 4837
Table 1. Selected Bond Lengths (Å) and Angles (deg) for
1a-3a and 4
1a
2a
3a
4
(E1 ) S(1), (E1 ) S(1), (E1 ) O(1), (E1 ) S(1),
E2 ) S(2)) E2 ) O(1)) E2 ) O(2)) E2 ) S(2))
Ru(1)-E1
2.3091(10) 2.295(2)
1.990(2)
1.991(3)
1.789(3)
1.787(2)
1.655(3)
2.3878(12)
2.2466(14)
2.3081(11)
2.2307(13)
1.670(3)
Ru(1)-E2
2.2954(8)
2.2201(8)
2.2327(9)
1.669(2)
1.998(2)
2.2424(9)
1.762(2)
1.649(2)
Ge(1)-E1
Ge(1)-E2
Ru(1)-(η6-arene)
S(1)-C(41)
1.818(4)
Ru(1)-E1-Ge(1)
Ru(1)-E2-Ge(1)
E1-Ru(1)- E2
90.77(3)
90.81(3)
86.74(3)
90.49(3)
81.39(3)
103.63(11) 94.82(13)
83.79(7)
91.00(7)
94.81(12)
89.09(3)
94.76(5)
86.89(4)
89.28(5)
102.70(16)
104.50(17)
79.36(11)
90.59(13)
E1-Ge(1)- E2
Ru(1)-S(1)-C(41)
Ge(1)-S(1)-C(41)
dihedrala
11.6
4.4
6.5
2.5
a Dihedral angles between planes Ru-E1-E2 and Ge-E1-E2.
Figure 2. Molecular structure of Dmp(Dep)Ge(µ-S)(µ-SMe)Ru-
(η6-benzene) (4) with thermal ellipsoids drawn at the 40% level.
-
Scheme 2
Hydrogen atoms and the BF4 anion are omitted for clarity.
Scheme 3
perpendicularly to the Ru(1)-Ge(1) vector, and the four-
membered metallacycle assumes a planar geometry, as was
observed for 1a. The elongation of the Ru(1)-S(1) bond
(2.3878(12) Å) and concomitant shortening of the Ru(1)-S(2)
bond (2.2466(14) Å), relative to those of 1a (vide supra), are
understandable, because the S(1) pπ-Ru(1) d interaction
becomes weaker upon methylation at S(1). The methylation also
brought about the elongation of the Ge(1)-S(1) bond (2.3081(11)
Å) relative to that of 1a, while the Ge(1)-S(2) bond distance
is unchanged.
The coordinative unsaturation of 4 is manifested in its
reactions. When the purple complex 4 was dissolved in
acetonitrile, the solution turned brown, from which the aceto-
nitrile adduct 5 was isolated in quantitative yield. The 1H NMR
spectrum shows singlet signals at δ 1.41 for SMe and δ 2.11
for MeCN. The facile addition of MeCN is in contrast with the
robustness of 1b even in a refluxing acetonitrile solution,
indicating that the S-methylation enhances coordinative unsat-
uration of Ru.
the Ru-S and the Ru-O bonds is manifested by their short
bond distances in 1a (Ru-S ) 2.3091(10), 2.2954(8) Å), 2a
(Ru-S ) 2.295(2) Å, Ru-O ) 1.998(2) Å), and 3a (Ru-O )
1.990(2), 1.991(3) Å), which are similar to the Ru-S and the
Ru-O bond lengths of the reported electron-deficient ruthenium
thiolates and alkoxides, respectively.15,17,18 The short distances
between Ru and the η6-arene planes (1a, 1.669(2) Å; 2a,
1.649(2) Å; 3a, 1.655(3) Å) are also attributable to the electron
deficiency of the ruthenium. On the other hand, the Ge-S bond
distances of 1a (2.2201(8), 2.2327(9) Å) and 2a (2.2424(9) Å)
and the Ge-O bond distances of 2a (1.762(2) Å) and 3a
(1.789(3), 1.787(2) Å) are ordinary values for Ge-S and Ge-O
single bonds, respectively.10a,19,20
Methylation of 1b on µ-Sulfide. Treatment of 1b with
Me3OBF4 in CH2Cl2 afforded the monomethylated complex
Dmp(Dep)Ge(µ-S)(µ-SMe)Ru(η6-benzene) (4) in 64% yield as
purple crystals (Scheme 2). Further methylation did not take
place, even in the presence of excess Me3OBF4.
Reactions of 1a,b and 2a,b with PPh3 and PEt3. When a
toluene solution of 1a and PPh3 was heated to 100 °C for 10 h,
the solution changed from deep blue to orange. A standard
workup, followed by recrystallization from toluene/hexane, gave
the phosphine adduct Dmp(Dep)Ge(µ-S)2Ru(PPh3) (6) in 87%
yield as orange crystals (Scheme 3). In this reaction, the
p-cymene ligand was replaced by a mesityl group of Dmp, and
the coordination of PPh3 led to the 18-electron ruthenium
complex. A similar reaction of 1b, having the more labile η6-
benzene instead of η6-p-cymene, proceeded more quickly and
gave the same adduct, 6, in 82% yield within 5 h at 100 °C.
The PEt3 adduct 7 was also synthesized similarly in 87% yield
from 1a within 6 h at 80 °C.
In the UV-vis spectra, the CT band was observed at 548
nm, which is notably blue-shifted from the absorption maximum
of 1b. The H NMR spectrum shows the µ-SMe signal as a
sharp singlet at δ 1.83 with an integrated intensity of 3H,
indicating that one of the two bridging sulfurs is methylated.
According to the X-ray-derived structure of 4, as shown in
Figure 2, methylation occurred from the side opposite to Dmp,
probably to avoid steric congestion. The methyl group orients
1
(17) Ohki, Y.; Sadohara, H.; Takikawa, Y.; Tatsumi K. Angew. Chem.,
Int. Ed. 2004, 43, 2290.
(18) A similar electron-deficient ruthenium alkoxide complex, Cp*Ru-
(PCy3)OR (R ) CH2CF3 and SiPh3, Cy ) cyclohexyl), was reported to
have values of 2.0278(17) and 2.090(3) Å for the Ru-O distances.16a
(19) Baines, K. M.; Stibbs, W. G. Coord. Chem. ReV. 1995, 145, 157.
(20) The Ge-O bond distances of Dmp(Dep)Ge(OH)2 are 1.761(2) and
1.789(2) Å: unpublished results.
The reaction of Dmp(Dep)Ge(SLi)2 and the triphenylphos-
phine-coordinated ruthenium complex (η6-cymene)Ru(PPh3)-
Cl2 provided information on the phosphine-addition reaction

4838 Organometallics, Vol. 25, No. 20, 2006
Matsumoto et al.
Scheme 4
mechanism. After addition of (η6-p-cymene)Ru(PPh3)Cl2 to
Dmp(Dep)Ge(SLi)2 in THF at -70 °C, gradual warming of the
yellow solution caused the color change to deep blue, where
the generation of 1a was detected by UV-vis spectra. When
the crude blue product was heated to 100 °C in toluene
thereafter, the phosphine adduct 6 was obtained in 88% yield.
A mechanism consistent with the observations is depicted in
Scheme 4. The phosphine adduct Dmp(Dep)Ge(µ-S)2Ru(η6-p-
cymene)(PPh3) (A) may be involved as an intermediate in the
reaction of 1a and PPh3 as well as of that of (η6-p-cymene)-
Ru(PPh3)Cl2 and Dmp(Dep)Ge(SLi)2. The reverse reaction from
A to 1a would compete with an irreversible pathway to 6, where
1a is the kinetic product while 6 is the thermodynamic product.
1
In the H NMR spectrum of 6, two mesityl groups of Dmp
appeared independently, exhibiting two inequivalent singlets for
the four mesityl aromatic protons, two inequivalent singlets for
the four o-Me groups, and two inequivalent singlets for the two
p-Me groups at room temperature. Since these respective signals
did not show any signs of coalescing even at 70 °C in benzene-
d6, π-coordination of the mesityl ring to Ru is strong enough
to inhibit the exchange of the two mesityl groups in Dmp.
The reaction of 2a with PPh3 gave a similar adduct, Dmp-
(Dep)Ge(µ-S)(µ-O)Ru(PPh3) (8), as orange crystals in 84%
yield, although 3a and 3b having bis(µ-oxo) bridges did not
afford the corresponding adduct. Complex 8 decomposed slowly
in air, which is in contrast to the extremely stable bis(µ-sulfide)
Figure 3. Molecular structures of Dmp(Dep)Ge(µ-S)2Ru(PPh3) (6)
with thermal ellipsoids drawn at the 40% level: (a) side view, with
hydrogen atoms omitted for clarity; (b) top view, with hydrogen
atoms and PPh3 omitted for clarity.
1
complexes 6 and 7. The H NMR spectrum of 8 displays four
singlets for the mesityl aromatic protons and six singlets for
the mesityl methyl groups. The inequivalency is derived from
the asymmetric center at Ge as well as the fixation of the η6-
mesityl group on Ru.
Crystal Structures of Compounds 6 and 8. The molecular
structures of 6 and 8 are shown in Figures 3 and 4, respectively.
The geometry around Ru is an ordinary three-legged piano-
stool configuration capped by a mesityl group of Dmp in each
complex. The central four-membered metallacycles are ex-
tremely puckered, and the dihedral angle of 6 between the planes
of S(1)-Ge(1)-S(2) and S(1)-Ru(1)-S(2) is 46.8°, while the
corresponding dihedral angle of 8 is 40.4°. In complex 8, the
four-membered ring is rather strained, as indicated by the acute
Ru(1)-S(1)-Ge(1) angle (76.25(2)°), due to the µ-O atom,
which has a smaller bond radius relative to that of µ-S. The
Ru-S bond distances of 6 (2.4185(7) and 2.4007(8) Å) are
significantly longer compared to those of 1a and the coordina-
tively unsaturated ruthenium(II) thiolato complexes (Table
2).15,21 Similarly, the distances of Ru(1)-S(1) (2.4371(9) Å)
and Ru(1)-O(1) (2.075(2) Å) for 8 are longer than those for
2a (Table 3).22
Figure 4. Molecular structure of Dmp(Dep)Ge(µ-S)(µ-O)Ru(PPh3)
(8) with thermal ellipsoids drawn at the 40% level. Hydrogen atoms
are omitted for clarity.
A structural feature common to 6 and 8 is the distorted
m-terphenyl arrangement of Dmp. As is obvious from the top
view of 6 (Figure 3b), the projection of the two bonds that
conjunct the Dmp central aromatic ring and each mesityl group
is significantly deviated from a straight line. The distortion is
also obvious from the significantly large dihedral angle, 19.0°,
between the planes defined by C(5)-C(6)-C(16) and C(2)-
C(3)-C(7) for 6. As is observed for 1a-3a, as well as for
germanium compounds having both Dmp and Dep ligands such
as Dmp(Dep)GeSx (x ) 4, 6), Dep and a mesityl group of Dmp
prefer to assume an offset π-π stacked configuration.10b The
offset π-π stacking is reported to be thermodynamically
preferable and is observed in various π-π stacked aromatic
(21) For several examples of ruthenium(II) thiolate, see: (a) Coto, A.;
Rios, I. D. I.; Tenorio, M. J.; Puerta, M. C.; Valerga, P. J. Chem. Soc.,
Dalton Trans. 1999, 4309. (b) Bartucz, T. Y.; Golombek, A.; Lough, A. J.;
Maltby, P. A.; Morris, R. H.; Ramachandran, R.; Schlaf, M. Inorg. Chem.
1998, 37, 1555. (c) Huang, J.; Li, C.; Nolan, S. P.; Petersen, J. L.
Organometallics 1998, 17, 3516. (d) Burn, M. J.; Fickes, M. G.; Hollander,
F. J.; Bergman, R. G. Organometallics 1995, 14, 137.

Oxo- and Sulfido-Bridged Ge-Ru Complexes
Organometallics, Vol. 25, No. 20, 2006 4839
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 6,
9, and 12
Scheme 5
6
9
12
Ru(1)-S(1)
Ru(1)-S(2)
Ge(1)-S(1)
Ge(1)-S(2)
Ru(1)-P(1)
Ru(1)-(η6-Mes)
S(1)-R
2.4185(7)
2.4007(8)
2.2082(7)
2.2106(6)
2.3248(8)
1.742(2)
2.3682(6)
2.4133(7)
2.3227(6)
2.1905(6)
2.3516(7)
1.737(1)
1.23(3) (to
H(66))
2.4098(9)
2.4057(6)
2.3148(7)
2.2004(8)
2.3708(8)
1.773(2)
1.811(3) (to
C(53))
Ru(1)-S(1)-Ge(1)
Ru(1)-S(2)-Ge(1)
S(1)-Ru(1)-S(2)
S(1)-Ge(1)-S(2)
S(1)-Ru(1)-P(1)
S(2)-Ru(1)-P(1)
82.12(2)
82.48(2)
83.57(2)
93.23(3)
85.54(3)
87.08(2)
83.61(2)
85.43(2)
83.44(2)
89.62(2)
92.04(2)
85.46(2)
83.59(2)
86.15(2)
81.95(2)
88.71(2)
99.32(3)
87.08(2)
Scheme 6
dihedrala
46.8
45.2
46.9
a Dihedral angles between planes Ru(1)-S(1)-S(2) and Ge(1)-S(1)-
S(2).
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 8
and 13
8
13
Ru(1)-S(1)
Ru(1)-O(1)
Ge(1)-S(1)
Ge(1)-O(1)
Ru(1)-P(1)
Ru(1)-(η6-Mes)
O(1)-H(66)
2.4371(9)
2.075(2)
2.2220(10)
1.770(2)
2.3526(11)
1.714(2)
2.4210(5)
2.1371(15)
2.1886(6)
1.8837(17)
2.3508(6)
1.7047(11)
0.84(3)
Ru(1)-S(1)-Ge(1)
Ru(1)-O(1)-Ge(1)
S(1)-Ru(1)-O(1)
S(1)-Ge(1)-O(1)
S(1)-Ru(1)-P(1)
O(1)-Ru(1)-P(1)
76.25(2)
96.73(10)
79.60(6)
92.54(8)
90.64(3)
88.90(7)
79.672(18)
94.54(6)
79.57(4)
91.51(4)
88.86(2)
89.03(4)
dihedrala
40.5
40.3
a Dihedral angles between planes Ru(1)-S(1)-O(1) and Ge(1)-S(1)-
O(1).
nated. Addition of HOTf to 6 also gave the same protonated
compound 11, having a triflate as a counteranion instead of
compounds.23 In 6 and 8, configurations having a greater overlap
of Dep and a mesityl group would be quite unfavorable, due to
the large steric repulsion between their o-alkyl substituents.
Since the Dmp group of 6 or 8 includes another mesityl group
which is coordinated onto Ru fixed by two µ-sulfides, it assumes
a deformed m-terphenyl configuration.
BArF .
4
The S-H stretching bands of 9 were observed in the Raman
1
and IR spectra at 2490 and 2489 cm-1, respectively. The H
NMR spectrum shows the µ-SH signal at δ -0.33 as a doublet
with JP-H ) 6.9 Hz. The assignment was confirmed by treatment
of 9 with D2O, which caused the facile disappearance of the
Protonation and Methylation Reactions of 6-8. To a
dichloromethane solution of 6 and 7 was added 1 equiv of
1
signal in the H NMR spectra.
The reaction of 6 with Me3OBF4 in dichloromethane also
H(OEt2)2BArF to give the protonated cationic compounds 9
4
proceeded similarly to give the monomethylated cationic
(72% yield) and 10 (61% yield) as yellow crystals, respectively
(Scheme 5). In either reaction, one µ-S was selectively proto-
1
complex 12 in 62% yield. The H NMR spectrum exhibits a
singlet for SMe at δ 0.71, which resonates at higher magnetic
field compared to the normal SMe proton region. This is
probably due to the anisotropic effect of the phenyl groups of
PPh3, which stay close to SMe, as is obvious from the crystal
structure (vide infra).
(22) For several examples of ruthenium(II) alkoxide, aryloxide, and
siloxide, see: (a) Yip, K.-L.; Yu, W.-Y.; Chan, P.-M.; Zhu, N.-Y.; Che,
C.-M. Dalton Trans. 2003, 3556. (b) Hirano, T.; Oi, T.; Nagano, H.;
Morokuma, K. Inorg. Chem. 2003, 42, 6575. (c) Lai, Y.-H.; Chou, T.-Y.;
Song, Y.-H.; Liu, C.-S.; Chi, Y.; Carty, A. J.; Peng, S.-M.; Lee, G.-H. Chem.
Mater. 2003, 15, 2454. (d) Hennig, M.; Puntener, K.; Scalone, M.
Tetrahedron: Asymmetry 2000, 11, 1849. (e) Casey, C. P.; Singer, S. W.;
Powell, D. R.; Hayashi, R. K.; Kavana, M. J. Am. Chem. Soc. 2001, 123,
1090. (f) Everaere, K.; Mortreux, A.; Bulliard, M.; Brussee, J.; van der
Gen, A.; Nowogrocki, G.; Carpentier, J.-F. Eur. J. Org. Chem. 2001, 275.
(g) Onitsuka, K.; Ajioka, Y.; Matsushima, Y.; Takahashi, S. Organometallics
2001, 20, 3274. (h) Rath, R. K.; Nethaji, M.; Chakravarty, A. R. Polyhedron
2001, 20, 2735. (i) Brunner, H.; Zwack, T.; Zabel, M.; Beck, W.; Bo¨hm,
A. Organometallics 2003, 22, 1741. (j) Stobart, S. R.; Zhou, X.; Cea-
Olivares, R.; Toscano, A. Organometallics 2001, 20, 4766.
As for the protonation of 8 having oxo/sulfido bridges, the
oxo bridge was selectively protonated. Addition of H(OEt2)2-
BArF or HOTf to 8 in toluene afforded 13 or 14 in 85% and
4
88% yield, respectively (Scheme 6). All the spectral data support
their µ-OH structure. The IR spectra did not show the S-H
stretching band that was clearly observed for the µ-SH complex
9. In the 1H NMR spectra of 13 and 14, the signals at δ -1.01
and 0.66 assigned to the µ-OH protons were observed as a
singlet, respectively, while the µ-SH signal of either 9 or 10
appeared as a doublet due to the proton-phosphorus coupling.
(23) (a) Janiak, C. Dalton Trans. 2000, 3885. (b) Lorenzo, S.; Lewis,
G. R.; Dance, I. New J. Chem. 2000, 24, 295.

4840 Organometallics, Vol. 25, No. 20, 2006
Matsumoto et al.
The absence of coupling between the phosphorus and the µ-OH
proton may be attributed to the weak interaction between Ru
and OH, as is shown in the X-ray-derived structure of 13 (vide
infra).
In contrast to the protonation reaction, methylation of 8
occurred at the sulfido bridge selectively. Treatment with methyl
trifluoromethanesulfonate in ether afforded the monomethylated
product as a yellow powder in 52% yield, which was identified
as [Dmp(Dep)Ge(µ-SMe)(µ-O)Ru(PPh3)](OTf) (15). Although
we failed to crystallize 15, the X-ray structural analysis of 16
that formed by hydrolyzation of 15 obviously shows the
S-selective methylation of 8.24 The S-methylated complex 15
was hydrolyzed at the Ge-SMe bond, and the subsequent
formation of the intermolecular bis(µ-SMe) bridges at the
ruthenium centers with concomitant PPh3 dissociation would
afford 16.
The properties of µ-sulfide and µ-oxide of 8 can be sum-
marized as follows. The µ-sulfide of 8 shows higher nucleo-
philicity relative to the µ-oxide. Meanwhile, the µ-oxide is more
basic compared to the µ-sulfide. These characteristic properties
are reasonable according to the HSAB (hard and soft acid-
base) principle25 and also fit the known results that alkanethiols
and protonated alkyl thioethers show higher acidity relative to
the corresponding alcohols and protonated alkyl ethers, respec-
tively.26
Figure 5. Molecular structure of [Dmp(Dep)Ge(µ-S)(µ-SMe)-
RuPPh3](BF4) (12) with thermal ellipsoids drawn at the 40% level.
Hydrogen atoms, dichloromethane, and the BF4- anion are omitted
for clarity.
Crystal Structures of Compounds 9, 12, and 13. X-ray
structures of 9, 12, and 13 reveal the unique properties of the
cationic Ge-Ru complexes. Of interest is their characteristic
geometrical changes around the chalcogen bridges. The S(1)-
protonated complex 9 has a shorter Ru(1)-S(1) bond distance
(2.3682(6) Å) compared to that of the Ru(1)-S(2) bond
(2.4133(7) Å) and to those of the Ru-S bonds for 6 (Table 2).
A similar M-S bond shortening upon S-alkylation of coordi-
natively saturated metal thiolato complexes has been re-
ported.10,27 The bond shortening would be due to the elimination
of repulsive interactions between the filled d orbitals on the
metals and the sulfur lone pair, although the lower σ-donor
properties of the sulfur atom could increase the M-S bond
distance concurrently.27
Figure 6. Molecular structure of [Dmp(Dep)Ge(µ-S)(µ-OH)-
RuPPh3](BArF ) (13) with thermal ellipsoids drawn at the 40% level.
4
Hydrogen atoms, toluene, and the BArF - anion are omitted for
4
clarity.
Scheme 7
On the other hand, the corresponding Ru(1)-S(1) bond of
the S(1)-methylated complex 12 does not become shorter, having
a distance similar to that of the Ru(1)-S(2) bond (Figure 5,
Table 2). This might be because the steric repulsion between
SMe and PPh3 hampers the Ru(1)-S(1) bond shortening, as is
suggested by the X-ray structure in Figure 5. The steric
congestion around the SMe group is evident in the larger bond
angle of S(1)-Ru(1)-P(1) (99.32(3)°) compared to that of the
protonated complex 9 (92.04(2)°). Furthermore, the S(1)-C(53)
vector is directed toward the germanium side due to steric
congestion.
In contrast to the Ru-S bond shortening upon protonation,
the O-protonation brought about a significant Ru-O bond
elongation from 2.075(2) Å for 8 to 2.1371(15) Å for 13. This
result indicates that the σ-donor ability of O greatly affects the
Ru-O bond, while the decreased repulsive π-orbital interaction
may be less important here.
bond distances of 9 and 12 (2.3227(6) and 2.3148(7) Å) are
significantly longer than those of 6 as well as the reported Ge-S
single bonds,19 which indicates that the Ge-S bonds become
weak upon protonation/methylation of µ-S. Likewise, the Ge-O
bond is elongated upon protonation of the µ-oxide of 8 (Figure
6 and Table 3).
Reactions of the Methylated/Protonated Complexes 9, 12,
and 13 with NEt4Cl. The characteristic structural changes
caused by the protonation and the methylation were reflected
in the reactivities of these complexes with NEt4Cl. Reaction of
the µ-OH complex 13 with NEt4Cl in THF took place im-
mediately at room temperature, and the Ru-O bond was cleaved
by nucleophilic Cl- addition at Ru to afford the ruthenium-
chloride complex 17 (Scheme 7). Reaction of the µ-oxo/µ-
sulfido complex 8 with HCl in ether also afforded 17 in 83%
yield. The stereochemistry of 17 was confirmed by X-ray
structural analysis. Another diastereomer was not observed,
probably due to its steric congestion. The Cl- - -O distance of
17 (3.25(1) Å) indicates the O-H- - -Cl hydrogen bonding,
which could also facilitate the formation of 17.9a
The bond elongations between the germanium and the
protonated/methylated sulfur are also notable. The Ge(1)-S(1)
(24) Although the structure of 16 is evident from the X-ray analysis, the
other possible diastereomers could be generated by hydrolyzation reactions
1
of 15. The H NMR spectrum of the crude product is too complicated to
allow identification of all the signals.
(25) Pearson, R. G. J. Chem. Educ. 1968, 45, 643.
(26) Ho, T.-L. Chem. ReV. 1975, 75, 1.
(27) Ashby, M. T.; Enemark, J. H.; Lichtenberger, D. L. Inorg. Chem.
1988, 27, 191.

Oxo- and Sulfido-Bridged Ge-Ru Complexes
Organometallics, Vol. 25, No. 20, 2006 4841
Dmp(Dep)GeH2) as a white powder. 1H NMR (500 MHz, CDCl3):
δ 7.47 (t, J ) 7.8 Hz, 1H, p-CH of Dmp), 7.10 (t, J ) 7.8 Hz, 1H,
p-CH of Dmp), 7.04 (d, J ) 7.3 Hz, 2H, m-CH of Dmp), 6.79 (s,
2H, m-CH of Mes), 6.64 (s, 2H, m-CH of Mes), 2.49 (br q, J )
7.8 Hz, 4H, CH2CH3 of Dep), 2.25 (s, 6H, p-CH3 of Mes), 2.06 (s,
6H, o-CH3 of Mes), 1.93 (s, 6H, o-CH3 of Mes), 1.17 (s, 1H,
GeOH), 1.01 (t, J ) 7.8 Hz, 6H, CH2CH3 of Dep), 0.06 (s, 1H,
GeSH). Anal. Calcd for C34H40GeOS: C, 71.72; H, 7.08; S, 5.63.
Found: C, 71.66; H, 7.50; S, 5.56.
In contrast to the facile Ru-O dissociation, the S-protonated/
methylated complexes 9 and 12 either did not afford any adduct
by treatment with NEt4Cl, even at 60 °C in THF. The difference
in the reactivities of the µ-OH complex 13 and the µ-SH
complex 9 is due to the respective structural changes upon
protonation described above.
Summary
Synthesis of Dmp(Dep)Ge(OH)2. To a CH2Cl2 solution of Dmp-
(Dep)GeH2 (504.2 mg, 0.967 mmol) was added 3-chloroperoxy-
benzoic acid (500.7 mg, 2.90 mmol), and the mixture was stirred
overnight at room temperature. The resulting light yellow suspen-
sion was filtered, and the solution was separated by silica gel
chromatography (with 4/1 hexane/CH2Cl2) and recrystallized from
CH2Cl2/EtOH to afford Dmp(Dep)Ge(OH)2 as a white powder
(215.2 mg, 0.389 mmol, 40% yield). 1H NMR (500 MHz, CDCl3):
δ 7.50 (t, J ) 7.8 Hz, 1H, p-CH of Dmp), 7.11 (t, J ) 7.8 Hz, 1H,
p-CH of Dmp), 7.07 (d, J ) 7.3 Hz, 2H, m-CH of Dmp), 6.78 (d,
J ) 7.8 Hz, 2H, m-CH of Dmp), 6.74 (s, 4H, m-CH of Mes), 2.39
(dq, J ) 7.8 Hz, 14.2 Hz, 4H, CH2CH3 of Dep), 2.25 (s, 6H, p-CH3
of Mes), 2.00 (s, 12H, o-CH3 of Mes), 1.14 (s, 2H, GeOH), 1.00
(t, J ) 7.3 Hz, 6H, CH2CH3 of Dep). Anal. Calcd for C34H40GeO2:
C, 73.81; H, 7.29. Found: C, 73.80; H, 7.33.
We synthesized a series of µ-sulfido and µ-oxo heterodi-
nuclear germanium-ruthenium complexes, Dmp(Dep)Ge(µ-
E)2Ru(η6-arene) and Dmp(Dep)Ge(µ-S)(µ-E)Ru(PR3) (E ) O,
S), from the corresponding diarylgermanedichalcogenols, re-
spectively. The characteristic properties of the µ-oxide and the
µ-sulfide are represented by protonation and methylation
reactions. X-ray structural analysis reveals their characteristic
structural changes upon protonation and methylation around both
the ruthenium and the germanium atoms, which is in accordance
with their reactions. As is suggested from the reaction of the
dinuclear µ-OH complex with Cl-, the ruthenium and the
germanium work cooperatively through the bridging chalcogen
atom. The chalcogenido-bridged Ge-Ru complexes undergo
various new reactions via cooperation of Ge and Ru as well as
S and O.
Synthesis of Dmp(Dep)GeS2Ru(η6-p-cymene) (1a). To a THF
solution of Dmp(Dep)Ge(SH)2 (150 mg, 0.26 mmol) was added
n-BuLi (0.34 mL of a 1.6 M solution in hexane, 0.54 mmol) at
-78 °C, and the mixture was stirred for 30 min. [(η6-p-cymene)-
RuCl2]2 (79 mg, 0.13 mmol) was then added, and this mixture was
stirred at 25 °C for 12 h to give a dark blue solution. The solvent
was removed in vacuo, and the residue was treated with toluene (5
mL) and the solution centrifuged to remove LiCl. The toluene
solution was removed and crystallized from DME to give 1a as
Experimental Section
General Considerations. All reactions and manipulations of air-
sensitive compounds were conducted under an inert atmosphere of
dry nitrogen by employing standard Schlenk techniques. Toluene,
THF, diethyl ether, and hexane were distilled from sodium/
benzophenone ketyl under nitrogen. Dichloromethane, acetonitrile,
and hexamethyldisiloxane (HMDSO) were distilled from CaH2.
1H NMR (500 or 600 MHz) and 31P NMR spectra (202 or 243
MHz) were recorded on a JEOL JNM-ECP500 or ECA600
1
deep blue crystals in 87% yield. H NMR (500 MHz, C6D6): δ
7.19 (t, J ) 7.3 Hz, 1H, p-CH of Dmp), 7.08 (t, J ) 7.3 Hz, 1H,
p-CH of Dep), 6.93 (d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.84 (d,
J ) 7.3 Hz, 1H, m-CH of Dmp), 6.89 (s, 2H, m-CH of Mes), 6.81
(d, 1H, J ) 7.3 Hz, m-CH of Dep), 6.77 (s, 4H, m-CH of Mes),
4.71 (d, 2H, J ) 6.0 Hz, p-cymene arom), 4.57 (d, 2H, J ) 6.0
Hz, p-cymene arom), 3.34 (dq, J ) 7.3 Hz, 6.9 Hz, 2H, CH2CH3
of Dep), 2.68 (sept, J ) 6.9 Hz, 1H, p-cymene), 2.34 (dq, J ) 7.3
Hz, 6.9 Hz, 2H, CH2CH3 of Dep), 2.32 (s, 6H, CH3 of Mes), 2.27
(s, 12H , CH3 of Mes), 2.13 (s, 6H, CH3 of Mes), 1.93 (s, 3H,
p-cymene), 1.14 (d, J ) 6.9 Hz, 6H, p-cymene), 0.89 (t, J ) 6.9
Hz, 3H, Me of Dep). Anal. Calcd for C44H52GeRuS2: C, 64.55; H,
6.40; S, 7.83. Found: C, 64.16; H, 6.65; S, 7.51. UV-vis (THF):
λmax 658 nm (ꢀ 4.1 × 103).
1
spectrometer. H NMR chemical shifts are given in ppm relative
to the residual protons of deuterated solvents. 31P{1H} NMR
chemical shifts were referenced to signals of external 85% H3PO4.
IR spectra were recorded on a JASCO FT/IR-410 spectrometer.
Raman spectra were measured on a Perkin-Elmer Spectrum 2000
with a Nd YAG laser. For UV-vis spectra, a JUSCO V-560
spectrometer was used. Elemental analyses were performed on
LECO CHN-900 and CHNS-932 microanalyzers.
Synthesis of Dmp(Dep)Ge(SH)2. A THF/ethanol (20/1) solution
of Dmp(Dep)GeSx (x ) 4, 6) prepared by sulfurization of Dmp-
(Dep)GeH2 (1.0 g, 1.9 mmol)1 was treated with NaBH4 (150 mg,
4.0 mmol) at 0 °C. The mixture was stirred at room temperature
for 12 h. After treatment with aqueous 0.5 M HCl and extraction
with CH2Cl2, the organic layer was dried over MgSO4 and
evaporated to dryness. The residue was recrystallized from CH2-
Cl2/hexane to give Dmp(Dep)Ge(SH)2 (470 mg, 0.80 mmol, 42%
yield based on Dmp(Dep)GeH2) as a white powder. 1H NMR (500
MHz, CDCl3): δ 7.45 (t, J ) 7.8 Hz, 1H, p-CH of Dmp), 7.14 (t,
J ) 7.8 Hz, 1H, p-CH of Dmp), 7.01 (d, J ) 7.8 Hz, 2H, m-CH of
Dmp), 6.82 (d, J ) 7.8 Hz, 2H, m-CH of Dmp), 6.74 (s, 4H, m-CH
of Mes), 2.26 (dq, J ) 7.8 Hz, 14.2 Hz, 4H, CH2CH3 of Dep),
2.26 (s, 6H, p-CH3 of Mes), 1.97 (s, 12H, o-CH3 of Mes), 1.01 (t,
J ) 7.3 Hz, 6H, CH2CH3 of Dep), 0.52 (s, 2H, GeSH). Anal. Calcd
for C34H40GeS2: C, 69.76; H, 6.89; S, 10.95. Found: C, 69.55; H,
7.30; S, 10.28.
Synthesis of Dmp(Dep)Ge(SH)(OH). To a THF solution of
Dmp(Dep)GeSx (x ) 4, 6) prepared from Dmp(Dep)GeH2 (1.0 g,
1.9 mmol) was added H2O (1 mL) and PPh3 (1.5 g, 5.7 mmol) in
air. After the mixture was stirred at room temperature for 12 h, the
solution was evaporated to dryness and the residue was chromato-
graphed on silica gel eluted with 5/1 hexane/CH2Cl2 to give Dmp-
(Dep)Ge(SH)(OH) (550 mg, 0.97 mmol, 51% yield based on
Synthesis of Dmp(Dep)Ge(µ-S)2Ru(η6-benzene) (1b). The
synthesis of 1b was carried out as described for 1a, but using Dmp-
(Dep)Ge(SH)2 (100 mg, 0.17 mmol) and [(η6-benzene)RuCl2]2 (45
mg, 0.09 mmol). Compound 1b was isolated as deep blue crystals
1
in 84% yield. H NMR (500 MHz, C6D6): δ 7.18 (t, J ) 7.8 Hz,
1H, p-CH of Dmp), 7.08 (t, J ) 7.8 Hz, 1H, p-CH of Dep), 6.94
(d, J ) 7.8 Hz, 2H, m-CH of Dmp), 6.83 (d, J ) 7.8 Hz, 2H,
m-CH of Dep), 6.70 (s, 4H, m-CH of Mes), 4.74 (s, 6H, benzene),
3.27 (dq, J ) 7.3 Hz, 6.9 Hz, 2H, CH2CH3 of Dep), 2.34 (dq, J )
7.3 Hz, 6.9 Hz, 2H, CH2CH3 of Dep), 2.30 (s, 6H, CH3 of Mes),
2.27 (s, 12H, CH3 of Mes), 1.26 (t, J ) 7.4 Hz, 6H, CH2CH3 of
Dep). Anal. Calcd for C40H44GeRuS2: C, 63.00; H, 5.82; S, 8.41.
Found: C, 62.88; H, 5.77; S, 8.87. UV-vis (THF): λmax 660 nm
(ꢀ 3.8 × 103).
Synthesis of Dmp(Dep)Ge(µ-S)(µ-O)Ru(η6-p-cymene) (2a).
The synthesis of 2a was carried out as described for 1a, but using
Dmp(Dep)Ge(SH)(OH) (100 mg, 0.18 mmol) and [(η6-p-cymene)-
RuCl2]2 (55 mg, 0.09 mmol). Compound 2a was isolated as purple
1
crystals in 88% yield. H NMR (500 MHz, C6D6): δ 7.19 (t, J )
7.3 Hz, 1H, p-CH of Dmp), 7.09 (t, J ) 7.3 Hz, 1H, p-CH of Dep),

4842 Organometallics, Vol. 25, No. 20, 2006
Matsumoto et al.
6.95 (d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.94 (s, 2H, m-CH of
Mes), 6.83 (d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.82 (d, J ) 7.3
Hz, 1H, Dep arom), 6.78 (d, J ) 7.3 Hz, 1H, Dep arom), 6.61 (s,
2H, m-CH of Mes), 4.85 (d, J ) 5.0 Hz, 1H, p-cymene arom),
4.77 (d, J ) 5.0 Hz, 1H, p-cymene arom), 4.69 (d, J ) 5.0 Hz,
1H, p-cymene arom), 4.67 (d, J ) 5.0 Hz, 1H, p-cymene arom),
3.30 (dq, J ) 7.3 Hz, 6.9 Hz, 1H, CH2CH3 of Dep), 3.09 (dq, J )
7.3 Hz, 6.9 Hz, 1H, CH2CH3 of Dep), 2.65 (sept, 1H, J ) 6.9 Hz,
p-cymene), 2.44 (s, 6H, Mes), 2.40 (dq, J ) 7.3 Hz, 6.9 Hz, 1H,
CH2CH3 of Dep), 2.34 (s, 6H, Mes), 2.22 (dq, J ) 7.3 Hz, 6.9 Hz,
1H, CH2CH3 of Dep), 2.08 (s, 6H, Mes), 2.01 (s, 3H, p-cymene),
1.28 (d, J ) 6.9 Hz, 6H, p-cymene), 1.26 (br t, J ) 7.3 Hz, 3H,
CH2CH3 of Dep), 1.24 (br t, J ) 7.3 Hz, 3H, CH2CH3 of Dep).
Anal. Calcd for C44H52GeORuS: C, 65.76; H, 6.65; S, 3.99.
Found: C, 65.66; H, 6.64; S, 4.38. UV-vis (THF): λmax 598 nm
(ꢀ 3.4 × 103).
2 h. To the solution was added ether (15 mL) to give a purple
powder, which was washed with ether to afford 4 (38.4 mg, 0.0444
mmol, 64%). X-ray-quality crystals were grown by layering ether
1
onto a CH2Cl2 solution of 4 at room temperature. H NMR (500
MHz, C6D6): δ 7.47 (t, J ) 7.8 Hz, 1H, p-CH of Dmp), 7.18 (t, J
) 7.3 Hz, 1H, p-CH of Dep), 6.97 (d, J ) 7.3 Hz, 2H, m-CH of
Dmp), 6.90 (d, J ) 7.4 Hz, 1H, m-CH of Dep), 6.77 (d, J ) 7.4
Hz, 1H, m-CH of Dep), 5.96 (s. 6H, benzene), 2.48 (s, 3H, CH3 of
Mes), 2.18 (s, 3H, CH3 of Mes), 2.10 (s, 3H, CH3 of Mes), 1.83 (s,
3H, µ-SCH3), 1.8 (br s, 3H, CH3 of Mes), 1.66 (s, 3H, CH3 of
Mes), 1.36 (s, 3H, CH3 of Mes), 1.07 (t, J ) 7.8 Hz, 3H, CH2CH3
of Dep), 0.74 (t, J ) 7.8 Hz, 3H, CH2CH3 of Dep). UV-visible
(λmax, CH2Cl2): 548 nm. Anal. Calcd for C41H47BF4GeRuS2: C,
56.96; H, 5.48; S, 7.42. Found: C, 56.32; H, 5.62; S, 6.94. UV-
vis (THF): λmax 548 nm (ꢀ 3.4 × 103)
Synthesis of [Dmp(Dep)Ge(µ-S)(µ-SCH3)Ru(CH3CN)(η6-
C6H6)][BF4] (5). Compound 4 (35 mg, 0.040 mmol) was dissolved
in CH3CN (5.0 mL) and stirred at room temperature for 2 h. The
brown solution was evaporated to dryness, and the brown residue
was washed with ether to afford compound 5 as a brown powder
Synthesis of Dmp(Dep)Ge(µ-S)(µ-O)Ru(η6-benzene) (2b). The
synthesis of 2b was carried out as described for 1a, but using Dmp-
(Dep)Ge(SH)(OH) (100 mg, 0.18 mmol) and [(η6-benzene)RuCl2]2
(45 mg, 0.09 mmol). Compound 2b was isolated as purple crystals
1
1
in 81% yield. H NMR (500 MHz, C6D6): δ 7.17 (t, J ) 7.8 Hz,
in 86% yield. H NMR (500 MHz, CD3CN): δ 7.48 (t, J ) 7.8
1H, p-CH of Dmp), 7.08 (t, J ) 7.8 Hz, 1H, p-CH of Dep), 7.04
(d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.94 (d, J ) 7.3 Hz, 1H,
m-CH of Dmp), 6.89 (s, 2H, m-CH of Mes), 6.81 (d, J ) 7.8 Hz,
1H, m-CH of Dep), 6.78 (d, J ) 7.8 Hz, 1H, m-CH of Dep), 6.58
(s, 2H, m-CH of Mes), 4.86 (s, 6H, benzene), 2.40 (br m, 1H, CH2-
CH3 of Dep), 3.43 (dq, 1H, J ) 7.3 Hz, 6.9 Hz, CH2CH3 of Dep),
2.24 (br m, 1H, CH2CH3 of Dep), 3.06 (dq, J ) 7.3 Hz, 6.9 Hz,
1H, CH2CH3 of Dep), 2.43 (s, 6H, CH3 of Mes), 2.30 (s, 6H, CH3
of Mes), 2.13 (s, 6H, CH3 of Mes), 1.33 (t, J ) 7.3 Hz, 3H, CH2CH3
of Dep), 1.26 (t, J ) 7.3 Hz, 3H, CH2CH3 of Dep). Anal. Calcd
for C40H44GeORuS: C, 64.36; H, 5.94; S, 4.30. Found: C, 64.00;
H, 5.82; S, 4.65. UV-vis (THF): λmax 601 nm (ꢀ 3.0 × 103).
Hz, 1H, p-CH of Dmp), 7.28 (t, J ) 7.8 Hz, 1H, p-CH of Dep),
7.00-6.90 (m, 6H), 5.56 (s, 6H, benzene), 3.15 (dq, J ) 7.4 Hz,
14.2 Hz, 1H, CH2CH3 of Dep), 2.31 (dq, J ) 7.4 Hz, 14.2 Hz, 1H,
CH2CH3 of Dep), 2.08 (dq, J ) 7.4 Hz, 14.2 Hz, 1H, CH2CH3 of
Dep), 1.81 (dq, J ) 7.4 Hz, 14.2 Hz, 1H, CH2CH3 of Dep), 2.36
(br s, 6H, CH3 of Mes), 2.22 (br s, 6H, CH3 of Mes), 2.14 (br s,
6H, CH3 of Mes), 2.11 (s, 3H, CH3CN), 1.41 (s, 3H, SCH3), 0.90
(t, J ) 7.3 Hz, 6H, CH2CH3 of Dep). Anal. Calcd for C43H50NBF4-
GeRuS2: C, 57.04; H, 5.57; N, 1.55; S, 7.08. Found: C, 56.82; H,
5.98; N, 1.81; S, 6.55.
Reaction of 1a with PPh3. Compound 1a (100 mg, 0.122 mmol)
and PPh3 (34 mg, 0.13 mmol) were dissolved in toluene (5 mL)
and stirred at 100 °C for 16 h. All of the volatiles were removed
in vacuo, and the residue was crystallized from toluene/hexane to
afford compound 6 as orange crystals in 87% yield. 1H NMR (600
MHz, C6D6): δ 7.82 (br m, 6H, PPh3), 7.33 (t, J ) 7.5 Hz, 1H,
Dmp p-arom), 7.00 (br m, 9H, PPh3), 6.98 (t, J ) 7.5 Hz, 1H, Dep
p-arom), 6.96 (dd, J ) 7.5 Hz, 1.4 Hz, 1H, Dmp m-arom), 6.90
(dd, J ) 7.5 Hz, 1.4 Hz, 1H, Dmp m-arom), 6.66 (d, J ) 7.5 Hz,
2H, Dep m-arom), 6.35 (s, 2H, Mes arom), 4.44 (s, 2H, Mes arom),
3.61 (dq, J ) 14.4 Hz, 7.2 Hz, 2H, CH2CH3 of Dep), 2.43 (dq, J
) 14.4 Hz, 7.2 Hz, 2H, CH2CH3 of Dep), 2.29 (s, 6H, o-CH3 of
Mes), 2.21 (s, 6H, o-CH3 of Mes), 2.03 (s, 3H, p-CH3 of Mes),
1.26 (t, J ) 7.2 Hz, 6H, CH2CH3 of Dep), 0.91 (s, 3H, p-CH3 of
Mes). 31P{1H} NMR (243 Hz, C6D6): δ 44.38. Anal. Calcd for
C52H53GePRuS2: C, 65.97; H, 5.64; S, 6.77. Found: C, 65.71; H,
5.64; S, 6.59.
Synthesis of Dmp(Dep)Ge(µ-O)2Ru(η6-p-cymene) (3a). The
synthesis of 3a was carried out as described for 1a, but using Dmp-
(Dep)Ge(OH)2 (100 mg, 0.18 mmol) and [(η6-p-cymene)RuCl2]2
(55 mg, 0.09 mmol). Compound 3a was isolated as purple crystals
1
in 69% yield. H NMR (500 MHz, C6D6): δ 7.19 (t, J ) 7.3 Hz,
1H, p-CH of Dmp), 7.09 (t, J ) 7.3 Hz, 1H, p-CH of Dep), 6.95
(d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.88 (d, J ) 7.3 Hz, 1H,
m-CH of Dmp), 6.89 (s, 2H, m-CH of Mes), 6.81 (d, J ) 7.3 Hz,
1H, m-CH of Dep), 6.75 (s, 4H, m-CH of Mes), 4.68 (d, J ) 6.0
Hz, 2H, p-cymene arom), 4.55 (d, J ) 6.0 Hz, 2H, p-cymene arom),
3.40 (dq, J ) 7.3 Hz, 6.9 Hz, 2H, CH2CH3 of Dep), 2.68 (sept, J
) 6.9 Hz, 1H, p-cymene), 2.34 (dq, J ) 7.3 Hz, 6.9 Hz, 2H, CH2-
CH3 of Dep), 2.32 (s, 6H, CH3 of Mes), 2.29 (s, 12H, CH3 of Mes),
2.13 (s, 6H, CH3 of Mes), 1.93 (s, 3H, p-cymene), 1.14 (d, J ) 6.9
Hz, 6H, p-cymene), 0.93 (t, J ) 6.9 Hz, 3H, Me of Dep). Anal.
Calcd for C44H52GeO2Ru: C, 67.19; H, 6.66. Found: C, 67.05; H,
6.69. UV-vis (THF): λmax 475 nm (ꢀ 2.5 × 103).
Reaction of 1b with PPh3. Compound 1b (100 mg, 0.131 mmol)
and PPh3 (37 mg, 0.14 mmol) were dissolved in toluene (5 mL)
and stirred at 100 °C for 5 h. All of the volatiles were removed in
vacuo and crystallized from toluene/hexane to afford 6 as orange
crystals in 82% yield.
Synthesis of Dmp(Dep)Ge(µ-O)2Ru(η6-benzene) (3b). The
synthesis of 3b was carried out as described for 1a, but using Dmp-
(Dep)Ge(OH)2 (107 mg, 0.19 mmol) and [(η6-benzene)RuCl2]2 (49
mg, 0.097 mmol). Compound 3b was isolated as purple crystals in
63% yield. 1H NMR (500 MHz, C6D6): δ 7.14 (t, J ) 7.8 Hz, 1H,
p-CH of Dmp), 7.11 (t, J ) 7.8 Hz, 1H, p-CH of Dmp), 6.89 (d,
J ) 7.3 Hz, 2H, m-CH of Dmp), 6.82 (d, J ) 7.3 Hz, 2H, m-CH
of Dep), 6.74 (s, 4H, m-CH of Mes), 4.83 (s, 6H, η6-C6H6), 3.30
(dq, J ) 7.8 Hz, 14.2 Hz, 2H, CH2CH3 of Dep), 2.39 (dq, J ) 7.8
Hz, 14.2 Hz, 2H, CH2CH3 of Dep), 2.28 (s, 6H, p-CH3 of Mes),
2.27 (s, 12H, o-CH3 of Mes), 1.35 (t, J ) 7.8 Hz, 6H, CH2CH3 of
Dep). Anal. Calcd for C40H44GeO2Ru: C, 65.77; H, 6.07. Found:
C, 66.02; H, 6.00. UV-vis (THF): λmax 476 nm (ꢀ 2.0 × 103).
Reaction of 1a with PEt3. Compound 1a (100 mg, 0.121 mmol)
and PEt3 (0.090 mL of 20% solution in toluene, 0.14 mmol) were
dissolved in toluene (5 mL), and the mixture was stirred at 80 °C
for 6 h. All of the volatiles were removed in vacuo and crystallized
from toluene/hexane to afford 7 as orange crystals in 87% yield.
1H NMR (600 MHz, C6D6): δ 7.37 (t, J ) 7.5 Hz, 1H, Dmp
p-arom), 7.03 (t, J ) 7.5 Hz, 1H, Dep p-arom), 7.02 (dd, J ) 7.5
Hz, 1.4 Hz, 1H, Dmp m-arom), 6.95 (dd, J ) 7.5 Hz, 1.4 Hz, 1H,
Dmp m-arom), 6.76 (d, J ) 7.5 Hz, 2H, Dep m-arom), 6.43 (s,
2H, Mes arom), 4.30 (s, 2H, Mes arom), 3.88 (dq, J ) 14.4 Hz,
7.2 Hz, 2H, CH2CH3 of Dep), 2.58 (dq, J ) 14.4 Hz, 7.2 Hz, 2H,
CH2CH3 of Dep), 2.33 (s, 6H, o-CH3 of Mes), 2.23 (s, 6H, o-CH3
of Mes), 2.11 (s, 3H, p-CH3 of Mes), 1.90 (dq, JH-H ) 7.5 Hz,
JP-H ) 7.5 Hz, 6H, PCH2CH3), 1.60 (t, J ) 7.2 Hz, 6H, CH2CH3
Synthesis of [Dmp(Dep)Ge(µ-S)(µ-SCH3)Ru(η6-C6H6)][BF4]
(4). Compound 1b (53.2 mg, 0.0697 mmol) and trimethyloxonium
tetrafluoroborate (11.1 mg, 0.0750 mmol) were dissolved in CH2-
Cl2 (5.0 mL), and the mixture was stirred at room temperature for

Oxo- and Sulfido-Bridged Ge-Ru Complexes
Organometallics, Vol. 25, No. 20, 2006 4843
of Dep), 0.99 (dt, JH-H ) 7.5 Hz, JP-H ) 15.0 Hz, 9H, PCH2CH3),
0.50 (s, 3H, p-CH3 of Mes). 31P{1H} NMR (243 Hz, C6D6): δ
26.82. Anal. Calcd for C40H53GePRuS2: C, 59.86; H, 6.66; S, 7.99.
Found: C, 59.67; H, 6.64; S, 7.65.
14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.24 (s, 3H, CH3 of Mes),
2.20 (s, 3H, CH3 of Mes), 1.95 (s, 3H, CH3 of Mes), 1.91 (s, 3H,
CH3 of Mes), 1.89 (s, 3H, CH3 of Mes), 1.16 (s, 3H, CH3 of Mes),
1.12 (t, J ) 7.2 Hz, 3H, CH2CH3 of Dep), 0.78 (t, J ) 7.2 Hz, 3H,
CH2CH3 of Dep), -0.45 (d, JP-H ) 6.4 Hz, 1H, µ-SH). 31P{1H}
Reaction of 2a with PPh3. Compound 2a (100 mg, 0.124 mmol)
and PPh3 (37 mg, 0.14 mmol) were dissolved in toluene (5 mL),
and the mixture was stirred at 100 °C for 16 h. All of the volatiles
were removed in vacuo and crystallized from toluene/hexane to
afford compound 8 as orange crystals in 87% yield. 1H NMR (500
MHz, C6D6): δ 7.86 (br m, 6H, PPh3), 7.35 (t, J ) 7.3 Hz, 1H,
p-CH of Dmp), 7.17 (t, J ) 7.3 Hz, 1H, p-CH of Dep), 7.05-7.00
(m, 9H, PPh3), 6.94 (d, J ) 7.3 Hz, 1H, m-CH of Dmp), 6.92 (d,
J ) 7.3 Hz, 1H, m-CH of Dmp), 6.80 (d, J ) 7.8 Hz, 1H, m-CH
of Dep), 6.64 (d, J ) 7.8 Hz, 1H, m-CH of Dep), 6.62 (s, 1H,
m-CH of Mes), 6.17 (s, 1H, m-CH of Mes), 4.37 (s, 1H, m-CH of
Mes), 4.32 (s, 1H, m-CH of Mes), 3.42 (dq, J ) 15.0 Hz, 7.5 Hz,
1H, CH2CH3 of Dep), 3.31 (dq, J ) 15.0 Hz, 7.5 Hz, 1H, CH2CH3
of Dep), 2.55 (dq, J ) 15.0 Hz, 7.5 Hz, 1H, CH2CH3 of Dep),
2.41 (s, 3H, CH3 of Mes), 2.27 (s, 3H, CH3 of Mes), 2.26 (dq, J )
15.0 Hz, 7.5 Hz, 1H, CH2CH3 of Dep), 2.14 (s, 3H, CH3 of Mes),
2.07 (s, 3H, CH3 of Mes), 2.01 (s, 3H, CH3 of Mes), 1.19 (t, J )
7.3 Hz, 3H, CH2CH3 of Dep), 1.26 (t, J ) 7.3 Hz, 3H, CH2CH3 of
Dep), 0.98 (s, 3H, CH3 of Mes). 31P{1H} NMR (202 MHz, C6D6):
δ 39.17. Anal. Calcd for C52H53GeOPRuS: C, 67.11; H, 5.74; S,
3.45. Found: C, 66.86; H, 5.97; S, 3.24.
NMR (202 MHz, CDCl3): δ 45.15. IR (KBr disk): 2490 cm-1
.
.
Raman (solid, excitation; Nd:YAG laser 1064 nm): 2489 cm-1
Anal. Calcd for C53H54F3GeO3PRuS3: C, 58.04; H, 4.96; S, 8.77.
Found: C, 58.46; H, 4.68; S, 8.29.
Protonation of 7 by H(OEt2)2BArF . To a diethyl ether solution
4
of 7 (45 mg, 0.048 mmol) was added H(OEt2)2BArF4 (51 mg, 0.50
mmol), and the mixture was stirred for 10 h at room temperature.
All the volatiles were removed in vacuo, and the residue was
washed with hexane. The orange powder was recrystallized from
toluene/HMDSO to give [Dmp(Dep)Ge(µ-S)(µ-SH)Ru(PEt3)]BArF
(10) as orange crystals in 61% yield. H NMR (600 MHz, C6D6):
4
1
δ 8.44 (s, 8H, ArF), 7.73 (s, 4H, ArF), 7.25 (t, J ) 7.5 Hz, 1H,
Dmp p-arom), 6.91 (t, J ) 7.5 Hz, 1H, Dep p-arom), 6.87 (d, J )
7.5 Hz, 1H, Dmp m-arom), 6.74 (d, J ) 7.5 Hz, 1H, Dmp m-arom),
6.63 (d, J ) 7.5 Hz, 1H, Dep m-arom), 6.57 (d, J ) 7.5 Hz, 1H,
Dep m-arom), 6.29 (s, 1H, Mes arom), 6.15 (s, 1H, Mes arom),
4.28 (s, 1H, Mes arom), 3.87 (s, 1H, Mes arom), 3.11 (dq, J )
14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.57 (dq, J ) 14.4 Hz, 7.2
Hz, 1H, CH2CH3 of Dep), 2.36 (dq, J ) 14.4 Hz, 7.2 Hz, 1H,
CH2CH3 of Dep), 2.26 (dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of
Dep), 2.00 (s, 3H, CH3 of Mes), 1.93 (s, 3H, CH3 of Mes), 1.89 (s,
3H, CH3 of Mes), 1.65 (s, 3H, CH3 of Mes), 1.51 (s, 3H, CH3 of
Mes), 1.43 (s, 3H, CH3 of Mes), 1.28-1.12 (m, 6H, PCH2CH3),
1.22 (t, J ) 7.2 Hz, 3H, CH2CH3 of Dep), 1.18 (t, J ) 7.2 Hz, 3H,
CH2CH3 of Dep), 0.52 (dt, JH-H ) 7.5 Hz, JP-H ) 15.0 Hz, 9H,
PCH2CH3), -0.47 (d, JP-H ) 4.9 Hz, 1H, µ-SH). 31P{1H} NMR
(243 Hz, C6D6): δ 27.31. IR (KBr disk): 2482 cm-1. Anal. Calcd
for C72H66BF24GePRuS2: C, 51.88; H, 3.99; S, 3.85. Found: C,
51.24; H, 4.28; S, 3.45.
Protonation of Compound 6 by H(OEt2)2BArF . To a diethyl
4
ether solution of compound 6 (50 mg, 0.053 mmol) was added
H(OEt2)2BArF (55 mg, 0.54 mmol), and the mixture was stirred
4
for 10 h at room temperature. All of the volatiles were removed in
vacuo, and the residue was washed with hexane. The orange powder
was recrystallized from toluene/HMDSO to give [Dmp(Dep)Ge-
(µ-S)(µ-SH)Ru(PPh3)]BArF (9) as orange crystals in 72% yield.
4
1H NMR (600 MHz, C6D6): δ 8.45 (s, 8H, ArF), 7.70 (s, 4H, ArF),
7.33-7.27 (m, 6H, PPh3), 7.28 (t, J ) 7.5 Hz, 1H, Dmp p-arom),
6.97 (br m, 9H, PPh3), 6.84 (dd, J ) 7.5 Hz, 1.4 Hz, 1H, Dmp
m-arom), 6.83 (t, J ) 7.5 Hz, 1H, Dep p-arom), 6.81 (dd, J ) 7.5
Hz, 1.4 Hz, 1H, Dmp m-arom), 6.47 (d, J ) 7.5 Hz, 1H, Dep
m-arom), 6.44 (d, J ) 7.5 Hz, 1H, Dep m-arom), 6.23 (s, 1H, Mes
arom), 6.13 (s, 1H, Mes arom), 4.70 (s, 1H, Mes arom), 4.15 (s,
1H, Mes arom), 2.90 (dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of
Dep), 2.30 (dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.20
(dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.16 (dq, J )
14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 1.93 (s, 3H, CH3 of Mes),
1.88 (s, 3H, CH3 of Mes), 1.87 (s, 3H, CH3 of Mes), 1.85 (s, 3H,
CH3 of Mes), 1.61 (s, 3H, CH3 of Mes), 0.59 (s, 3H, CH3 of Mes),
1.04 (t, J ) 7.2 Hz, 3H, CH2CH3 of Dep), 0.75 (t, J ) 7.2 Hz, 3H,
CH2CH3 of Dep), -0.33 (d, JP-H ) 3.1 Hz, 1H, µ-SH). IR (KBr
Synthesis of [Dmp(Dep)Ge(µ-S)(µ-SCH3)RuPPh3][BF4] (12).
Compound 6 (70 mg, 0.067 mmol) and trimethyloxonium tetra-
fluoroborate (12 mg, 0.081 mmol) were dissolved in CH2Cl2 (10
mL), and the mixture was stirred at room temperature for 10 h. All
of the volatiles were removed in vacuo, and the residue was washed
with diethyl ether to afford [Dmp(Dep)Ge(µ-S)(µ-SCH3)RuPPh3]-
[BF4] (12) as a yellow powder in 62% yield. X-ray-quality crystals
were grown by layering of diethyl ether onto the CH2Cl2 solution
at room temperature. 1H NMR (500 MHz, CDCl3): δ 7.68 (t, J )
7.3 Hz, 1H, p-CH of Dmp), 7.62 (br m, 6H, PPh3), 7.42 (br m, 9H,
PPh3), 7.33 (dd, J ) 6.9 Hz, 0.9 Hz, 1H, m-CH of Dmp), 7.18 (dd,
J ) 6.9 Hz, 0.9 Hz, 1H, m-CH of Dmp), 6.97 (t, J ) 7.3 Hz, 1H,
p-CH of Dep), 6.70 (d, J ) 7.3 Hz, 1H, m-CH of Dep), 6.55 (d, J
) 7.3 Hz, 1H, m-CH of Dep), 6.47 (s, 1H, m-CH of Mes), 6.11 (s,
1H, m-CH of Mes), 5.67 (s, 1H, m-CH of Mes), 4.44 (s, 1H, m-CH
of Mes), 2.80 (dq, J ) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep),
2.31 (dq, J ) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 2.31 (dq, J
) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 2.20 (s, 3H, CH3 of
Mes), 2.18 (s, 3H, CH3 of Mes), 2.13 (s, 3H, CH3 of Mes), 1.94 (s,
3H, CH3 of Mes), 1.91 (s, 3H, CH3 of Mes), 1.18 (s, 3H, CH3 of
Mes), 1.12 (t, J ) 7.8 Hz, 3H, CH2CH3 of Dep), 0.74 (t, J ) 7.8
Hz, 3H, CH2CH3 of Dep), 0.71 (br s, 3H, SCH3). Anal. Calcd for
C53H56BF4GeRuS2‚CH2Cl2: C, 57.21; H, 5.16; S, 5.60. Found: C,
56.82; H, 5.29; S, 5.40.
disk) 2490 cm-1 31P{1H} NMR (243 Hz, C6D6): δ 44.33. Anal.
.
Calcd for C84H66BF24GePRuS2: C, 55.71; H, 3.67; S, 3.54.
Found: C, 55.59; H, 3.66; S, 3.22.
Protonation of Compound 6 by HOTf. To a dichloromethane
solution of compound 6 (112 mg, 0.118 mmol) was added HOTf
(0.22 mL of 0.54 M dichloromethane solution, 0.12 mmol), and
the mixture was stirred for 12 h at room temperature. All of the
volatiles were removed in vacuo, and the yellow residue was washed
with ether to afford [Dmp(Dep)Ge(µ-S)(µ-SH)Ru(PPh3)]OTf (11)
in 96% yield. Single crystals suitable for X-ray analysis were grown
1
by layering of ether onto the dichloromethane solution. H NMR
(500 MHz, CDCl3): δ 7.70 (t, J ) 7.5 Hz, 1H, Dmp p-arom), 7.48-
7.32 (br m, 15H, PPh3), 7.43 (dd, J ) 7.5 Hz, 1.3 Hz, 1H, Dmp
m-arom), 7.14 (dd, J ) 7.5 Hz, 1.3 Hz, 1H, Dmp m-arom), 7.01 (t,
J ) 7.5 Hz, 1H, Dep p-arom), 6.65 (d, J ) 7.5 Hz, 1H, Dep
m-arom), 6.61 (d, J ) 7.5 Hz, 1H, Dep m-arom), 6.36 (s, 1H, Mes
arom), 6.19 (s, 1H, Mes arom), 5.58 (s, 1H, Mes arom), 5.10 (s,
1H, Mes arom), 2.88 (dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of
Dep), 2.31 (dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.26
(dq, J ) 14.4 Hz, 7.2 Hz, 1H, CH2CH3 of Dep), 2.22 (dq, J )
Synthesis of [Dmp(Dep)Ge(µ-S)(µ-OH)RuPPh3][BArF ] (13).
4
Compound 8 (31.3 mg, 0.0336 mmol) and H(Et2O)2BArF4 (70 mg,
0.0692 mmol) were dissolved in diethyl ether (5.0 mL), and the
mixture was was stirred at room temperature for 12 h. The orange
solution was evaporated to dryness, and the orange residue was
washed with hexane to afford 13 as a yellow-orange powder (51.4
mg, 0.0286 mmol, 85%). X-ray-quality crystals were grown by
layering of HMDSO onto the toluene solution. 1H NMR (500 MHz,
C6D6): δ 8.44 (s, 8H, o-CH of ArF), 7.71 (s, 4H, p-CH of ArF),

4844 Organometallics, Vol. 25, No. 20, 2006
Table 4. Crystal Data for Compounds 1a-3a, 4, 6, 8, 10, 12, 13, 16, and 17
Matsumoto et al.
1a
2a
3a‚0.5Et2O
4
6
8
formula
formula wt
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
C44H52GeRuS2
818.67
triclinic
C44H52GeORuS
802.61
C46H57GeO1.5RuS
823.62
C41H47BF4GeRuS2
864.41
monoclinic
C2/c (No. 15)
15.576(7)
C52H53GePRuS2
946.74
monoclinic
P21/c (No. 14)
22.292(2)
C52H53GeOPRuS
930.68
triclinic
monoclinic
P21/c (No. 14)
12.082(11)
15.324(14)
20.528(19)
triclinic
P1h (No. 2)
11.5964(16)
11.964(8)
16.076(13)
89.86(3)
88.00(3)
65.82(2)
2013.9(25)
2
P1h (No. 2)
11.5964(16)
11.817(3)
15.5409(18)
78.9528(13)
79.8165(13)
69.499(4)
1943.8(6)
2
1.399
12.984
848
55.1
P1h (No. 2)
11.5964(16)
12.8083(16)
16.8593(9)
82.603(3)
78.7029(10)
79.7565(12)
2177.1(5)
2
1.420
11.595
960
55.0
14.378(8)
34.35(2)
10.6693(12)
22.1440(4)
93.843(13)
90.87(2)
117.2224(4)
3792.0(60)
4
1.406
12.785
1664
7691(7)
8
1.493
13.308
3536
55.0
4683.5(7)
4
1.343
11.207
1952
55.4
Z
D
calcd, g cm-3
1.358
11.583
848
55.0
µ, cm-1
F000
2θmax, deg
no. of rflns
collected
indep (Rint
55.0
28 241
8895 (0.031)
485
0.0468
0.0943
1.406
30 219
8608 (0.043)
485
0.0407
0.1104
0.962
16 320
8487 (0.032)
530
0.0577
0.1369
1.294
38 280
8743 (0.044)
525
0.0545
0.1349
1.137
65 104
10 809 (0.040)
567
0.0417
0.0837
1.022
25 616
9829 (0.024)
571
0.0420
0.0957
1.155
)
no. of params
R1a
wR2b
GOF on F2 c
10
12‚CH2Cl2
13‚0.5Tol
16‚4THF
17‚0.5CHCl3
formula
C84H66BF24Ge-
PRuS2
1810.97
monoclinic
P21/n (No. 14)
20.770(4)
12.102(2)
31.916(6)
C54H58BCl2F4Ge-
PRuS2
1133.52
monoclinic
P21/n (No. 14)
15.802(2)
C
87.5H70BF24Ge-
OPRuS
C75H71BF24Ge-
O4RuS
1708.9
monoclinic
P21/c (No. 14)
14.703(5)
28.665(8)
19.456(6)
C
52.5H54Cl2.5Ge-
OPRuS
formula wt
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
1840.98
triclinic
P1h (No. 2)
12.5318(15)
17.246(2)
19.560(3)
84.988(4)
84.367(4)
75.790(3)
4069.5(9)
2
1026.33
triclinic
P1h (No. 2)
15.088(9)
17.308(12)
19.953(19)
104.69(3)
90.14(3)
91.929(16)
5037(7)
4
20.691(4)
16.6500(6)
95.255(3)
113.8913(10)
113.351(3)
7989(3)
4
1.506
7.379
3656
55.0
4977.4(11)
4
1.513
11.825
2320
7529(4)
4
1.508
7.346
3436
55.0
Z
D
calcd, g cm-3
1.502
7.019
1862
55.0
1.353
11.373
2106
55.0
µ, cm-1
F000
2θmax, deg
no. of rflns
collected
indep (Rint
55.2
80 156
18 296 (0.049)
1204
0.0409
0.1133
54 460
11 428 (0.043)
653
0.0364
0.0689
0.930
33 230
17 870 (0.024)
1165
0.0414
0.1080
59 133
17 221 (0.057)
1091
0.0874
0.1757
72 080
22 918 (0.035)
1207
0.0633
0.1591
)
no. of params
R1a
wR2b
GOF on F2 c
0.922
1.043
0.906
1.123
2
1/2
a R1 ) ∑||Fo| - |Fc||/∑|Fo| (I > 2σ(I)). b wR2 ) [(∑w(|Fo| - |Fc|)2/∑wFo )]1/2 (all data). c GOF ) [∑w(|Fo| - |Fc|)2/(No- Nv)]
(No ) number of
observations, Nv ) number of variables).
7.35 (br m, 6H, PPh3), 7.33 (t, J ) 7.8 Hz, 1H, p-CH of Dmp),
7.01-6.92 (br m, 9H, PPh3), 6.97 (d, J ) 6.9 Hz, 1H, m-CH of
Dep), 6.89 (d, J ) 6.9 Hz, 1H, m-CH of Dmp), 6.85 (t, J ) 7.8
Hz, 1H, p-CH of Dep), 6.48 (d, J ) 6.9 Hz, 2H, m-CH of Dmp),
6.39 (s, 1H, m-CH of Mes), 6.02 (s, 1H, m-CH of Mes), 4.54 (s,
1H, m-CH of Mes), 3.93 (s, 1H, m-CH of Mes), 2.75 (dq, J ) 7.4
Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 2.12 (dq, J ) 7.4 Hz, 14.8 Hz,
1H, CH2CH3 of Dep), 2.06 (s, 3H, CH3 of Mes), 2.03 (dq, J ) 7.4
Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 1.88 (s, 3H, CH3 of Mes), 1.86
(s, 3H, CH3 of Mes), 1.79 (s, 3H, CH3 of Mes), 1.56 (s, 3H, CH3
of Mes), 1.18 (dq, J ) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep),
0.95 (t, J ) 7.4 Hz, 3H, CH2CH3 of Dep), 0.60 (s, 3H, CH3 of
Mes), 0.32 (t, J ) 7.4 Hz, 3H, CH2CH3 of Dep), -1.01 (s, 1H,
µ-OH). 31P{1H} NMR (202 MHz, C6D6): δ 45.70. Anal. Calcd
for C84H66BF24GeOPRuS: C, 56.21; H, 3.71; S, 1.79. Found: C,
55.86; H, 3.99; S, 1.92.
solution was evaporated to dryness, and the yellow residue was
washed with diethyl ether to afford 14 as a yellow-orange powder
(99.5 mg, 0.0921 mmol, 88%). X-ray-quality crystals were grown
1
by layering of ether onto a THF solution at room temperature. H
NMR (500 MHz, C6D6): δ 7.72 (br m, 6H, PPh3), 7.32 (t, J ) 7.8
Hz, 1H, p-CH of Dmp), 7.00 (br m, 9H, PPh3), 6.79 (d, J ) 7.8
Hz, 2H, m-CH of Dmp), 6.74 (d, J ) 7.8 Hz, 1H, m-CH of Dep),
6.69 (d, J ) 7.8 Hz, 1H, m-CH of Dep), 6.77 (s, 1H, m-CH of
Mes), 6.16 (s, 1H, m-CH of Mes), 3.82 (s, 1H, m-CH of Mes),
3.44 (dq, J ) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 3.15 (dq, J
) 7.4 Hz, 14.8 Hz, 1H, CH2CH3 of Dep), 2.36 (s, 3H, CH3 of
Mes), 2.32 (s, 3H, CH3 of Mes), 2.14 (s, 3H, CH3 of Mes), 1.86 (s,
3H, CH3 of Mes), 1.77 (s, 3H, CH3 of Mes), 1.46 (s, 3H, CH3 of
Mes), 1.25 (t, J ) 7.8 Hz, 3H, CH2CH3 of Dep), 1.05 (t, J ) 7.8
Hz, 3H, CH2CH3 of Dep), 0.66 (s, 1H, µ-OH). Anal. Calcd for
C53H54F3GeO4PRuS2: C, 58.90; H, 5.04; S, 5.93. Found: C, 58.25;
H, 4.73; S, 6.11.
Synthesis of [Dmp(Dep)Ge(µ-S)(µ-OH)RuPPh3][OTf] (14). To
a diethyl ether solution of 8 (97.9 mg, 0.105 mmol) was added
TfOH (0.23 mL of 0.54 M ether solution, 0.123 mmol), and the
mixture was stirred at room temperature for 12 h. The yellow
Reaction of 8 with MeOTf. To a diethyl ether solution of 8
(65.4 mg, 0.0703 mmol) was added MeOTf (0.18 mL of 0.42 M
diethyl ether solution, 0.075 mmol), and the mixture was stirred

Oxo- and Sulfido-Bridged Ge-Ru Complexes
Organometallics, Vol. 25, No. 20, 2006 4845
for 12 h at room temperature. All of the volatiles were removed in
vacuo, and the yellow residue was washed with ether to afford
[Dmp(Dep)Ge(µ-SMe)(µ-O)Ru(PPh3)][OTf] (15) in 52% yield. 1H
NMR (500 MHz, C6D6): δ 7.67 (6H, m, PPh3), 7.31 (t, J ) 7.8
Hz, 1H, p-CH of Dmp), 7.16 (br m, 6H, PPh3), 7.00 (br m, 3H,
PPh3), 6.89 (t, J ) 7.8 Hz, 1H, p-CH of Dep), 6.77 (dd, J ) 1.4
Hz, 7.8 Hz, 1H, m-CH of Dep), 6.68 (d, J ) 7.8 Hz, 1H, m-CH of
Dmp), 6.56 (s, 1H, m-CH of Mes), 6.46 (s, 1H, m-CH of Mes),
6.38 (d, J ) 7.4 Hz, 1H, m-CH of Dmp), 5.95 (s, 1H, m-CH of
Mes), 3.94 (s, 1H, m-CH of Mes), 3.02 (dq, J ) 7.4 Hz, 14.2 Hz,
1H, CH2CH3 of Dep), 2.47 (s, 3H, CH3 of Mes), 2.29 (br s, 3H,
CH3), 1.95 (s, 3H, CH3 of Mes), 1.80 (s, 3H, CH3 of Mes), 1.78 (s,
3H, CH3 of Mes), 1.70 (s, 3H, CH3 of Mes), 1.62 (dq, J ) 7.4 Hz,
14.2 Hz, 1H, CH2CH3 of Dep), 1.40 (s, 3H, CH3 of Mes), 1.17 (t,
J ) 7.4 Hz, 3H, CH2CH3 of Dep), 0.71 (t, J ) 7.4 Hz, 3H, CH2CH3
of Dep). Anal. Calcd for C54H56F3GeO4PRuS2: C, 59.24; H, 5.16;
S, 5.86. Found: C, 58.89; H, 4.92; S, 5.48.
Reaction of 8 and HCl. To a toluene solution of 8 (200 mg,
0.215 mmol) was added HCl (1 M ether solution, 0.5 mmol), and
the mixture was stirred at room temperature. The solution was
treated as described above to afford 17 in 83% yield.
X-ray Structural Analysis. Crystallographic data are sum-
marized in Table 4. Crystals of 1a-3a, 4, 6, 8, 9, 12, 13, 16, and
17 were mounted on a loop using oil (CryoLoop, Immersion Oil,
Type B or Paraton, Hampton Research Corp.) and set on a Rigaku
AFC-8 instrument equipped with a ADSC Quantum 1 CCD detector
(for 1a, 4, 6, 8, 12, and 17), with a Mercury CCD detector (for 2a
and 3a), or with a Saturn CCD detector (for 16) or on a Rigaku
RA-Micro007 with a Saturn CCD detector (for 9 and 13). The
measurements were made by using graphite-monochromated Mo
KR radiation (λ ) 0.710 690 Å) under a cold nitrogen stream. The
frame data were integrated and corrected for absorption with the
MSC d*TREK program package for 1a, 6, 8, and 12 or with the
Rigaku/MSC CrystalClear package for 2a, 3a, 4, 9, 13, 16, and
17. The structures were solved with use of direct methods and
standard difference map techniques and were refined by full-matrix
least-squares procedures on F2 by a Rigaku/MSC CrystalStructure
package. Anisotropic refinement was applied to all non-hydrogen
atoms, but the disordered crystalline solvent molecules for 3a, 13,
and 17 (see Table 4) were refined isotropically. For 10, 13, and
{[Dmp(Dep)(OH)Ge(µ-OH)Ru]2(µ-SMe)2}[BArF ] (16). Anal.
4 2
Calcd for C134H110B2F48Ge2O4Ru2S2: C, 51.43; H, 3.54; S, 2.05.
Found: C, 51.80; H, 3.68; S, 1.87.
Reaction of 13 and NEt4Cl. To a THF solution of 13 (28 mg,
0.016 mmol) was added NEt4Cl (5.0 mg, 0.03 mmol), and the
mixture was stirred for 1 h at room temperature. The solvent was
evaporated, and the residue was chromatographed on silica gel
(eluted by ether) to afford Dmp(Dep)(OH)Ge(µ-S)RuCl(PPh3) (17)
16, some CF3 groups of BArF disordered over several positions
4
were also refined isotropically, in which the ratio was refined freely,
while the total occupancy of the components was constrained to
unity. The disordered hydrogen atoms of SH(66) in 9, OH(66) in
13, and OH(54,108) in 17 were assigned from the Fourier map
and refined isotropically. All of the other hydrogen atoms were
placed at calculated positions. Additional crystallographic data are
given in the Supporting Information.
1
quantitatively as a yellow powder. H NMR (500 MHz, CDCl3):
δ 7.75 (br m, 6H, Ph), 7.41 (t, J ) 7.3 Hz, 1H, p-CH of Dmp),
7.30 (br m, 9H, Ph), 7.08 (dd, J ) 7.3 Hz, 1.4 Hz, 1H, m-CH of
Dmp), 6.96 (t, J ) 7.3 Hz, 1H, p-CH of Dep), 6.93 (dd, J ) 7.3
Hz, 1.4 Hz, 1H, m-CH of Dmp), 6.75 (d, J ) 7.3 Hz, 1H, m-CH
of Dep), 6.67 (s, 1H, m-CH of Mes), 6.57 (d, J ) 7.3 Hz, 1H,
m-CH of Dep), 5.99 (s, 1H, m-CH of Mes), 5.45 (s, 1H, m-CH of
Mes), 4.03 (s, 1H, GeOH), 3.33 (dq, J ) 7.4 Hz, 14.2 Hz, 1H,
CH2CH3 of Dep), 3.24 (d, JP-H ) 2.8 Hz, 1H, m-CH of Mes), 2.34
(dq, J ) 7.4 Hz, 14.2 Hz, 1H, CH2CH3 of Dep), 2.14 (s, 3H, CH3
of Mes), 2.08 (s, 3H, CH3 of Mes), 2.00 (d, JP-H ) 2.3 Hz, 3H,
CH3 of Mes), 1.90 (dq, J ) 7.4 Hz, 14.2 Hz, 1H, CH2CH3 of Dep),
1.84 (s, 3H, CH3 of Mes), 1.75 (s, 3H, CH3 of Mes), 1.66 (s, 3H,
CH3 of Mes), 1.10 (t, J ) 7.4 Hz, CH2CH3 of Dep), 0.98 (t, J )
7.4 Hz, CH2CH3 of Dep). 31P{1H} NMR (202 MHz, CDCl3): δ
33.62. Anal. Calcd for C52H54ClGeOPRuS: C, 64.58; H, 5.63; S,
3.32. Found: C, 64.67; H, 5.84; S, 3.01.
Acknowledgment. This research was supported by Grants-
in-Aid from the Ministry of Education, Culture, Sports, Science
and Technology of Japan (Nos. 14078101 and 16750048).
Supporting Information Available: X-ray crystallographic data
for 1a-3a, 4, 6, 8, 9, 12, 13, 16, and 17 as CIF files. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM060449M