Synthesis and characterization of single thiolato-bridged heterodinuclear complexes: Irreversible isomerization of Cp(CO)2W(μ-SPh)(μ-cl) Ru(CO)(Cl)(PPh3) to Cp(CO)(Cl)W(μ-SPh)(μ-Cl)Ru(CO) 2(PPh3) via chloride an

Article abstract of DOI:10.1021/om800789m

Reaction between CpW(CO)₃SPh and RuCl₂(PPh ₃)_x (x = 3 and 4) in dichloromethane at room temperature afforded a single thiolato-bridged heterodinuclear complex, Cp(CO) ₂W(μ-SPh)(μ-Cl)Ru(CO)(CO)(Cl)(PPh

Full text of DOI:10.1021/om800789m

264
Organometallics 2009, 28, 264–269
Synthesis and Characterization of Single Thiolato-Bridged
Heterodinuclear Complexes: Irreversible Isomerization of
Cp(CO)2W(µ-SPh)(µ-Cl)Ru(CO)(Cl)(PPh3) to
Cp(CO)(Cl)W(µ-SPh)(µ-Cl)Ru(CO)2(PPh3) via Chloride and
Carbonyl Ligand Migration
Md. Munkir Hossain,† Hsiu-Mei Lin,§ Chih-Min Wang,†,‡ and Shin-Guang Shyu*,†,‡
Institute of Chemistry, Academia Sinica, Taipei, Taiwan, Republic of China, Department of Chemistry,
National Central UniVersity, Chungli, Taiwan, Republic of China, and Institute of Bioscience and
Biotechnology, National Taiwan Ocean UniVersity, Keelung, Taiwan, Republic of China
ReceiVed August 15, 2008
Reaction between CpW(CO)3SPh and RuCl2(PPh3)x (x ) 3 and 4) in dichloromethane at room temperature
afforded a single thiolato-bridged heterodinuclear complex, Cp(CO)2W(µ-SPh)(µ-Cl)Ru(CO)(Cl)(PPh3) (1)
in high yield. Irreversible isomerization of 1 to Cp(CO)(Cl)W(µ-SPh)(µ-Cl)Ru(CO)2(PPh3) (2), which exists
as a mixture of stereoisomers 2a and 2b, occurs via chloride and carbonyl ligand migration during thermolysis
of 1 in toluene at 80 °C. Compounds 1, 2a, and 2b were characterized by single-crystal X-ray diffraction
analysis. Migration of π-acceptor carbonyl ligands from W atom to Ru atom during the conversion of
CpW(CO)3SPh + RuCl2(PPh3)3 f 1 f 2 with concomitant migration of σ-donor chloride ligand from Ru to
W atom in 1 is reported.
carbonyl compounds, carbonyl migration between metals is very
common.1 However, significantly fewer studies on carbonyl
migration on heterometallic clusters than those on homometallic
clusters were reported.1 Furthermore, although the reversible
carbonyl ligand migration is usual in metal carbonyl clusters,
the irreversible migration of CO ligand from one metal to
another metal is less common.9
Chloride migration is a unique way to synthesize organic
molecules10 including biological conversion of trichloroethylene
to chloral by cytochrome P-450.11 Chloride ion can form a
bridging bond in clusters, but its migration on clusters and
dinuclear complexes is rare.12,13
Introduction
The dynamic behavior of ligands in fluxional molecules has
been well documented in the last three decades1 and has been
observed for organic, inorganic, and organometallic compounds.
Among them, ligand migration in organometallic complexes
containing metal-metal bonds is of special interest because such
occurrence and rationalization are appropriate models for a better
understanding of ligand migration in clusters and surface
mobility of chemisorbed species.2 Ligand migration occurs in
different ways, and metal to ligand and metal to metal migrations
are more common. Ligands such as acyl,3 alkoxycarbonyl,3e
formyl,3b 3c silyl,4 germyl,5 stannyl,5 plumbyl,5 hydride,6 phos-
,
phinate,7 and phosphorane8 were demonstrated to migrate from
Sulfides and phosphines are usual bridging ligands for binding
different metals. Thiolato-bridged complexes become more
significant over the phosphido-bridged ones when catalytic and
a transition metal to the ligand η5-cyclopentadienyl ring. In metal
* Corresponding author. E-mail: sgshyu@chem.sinica.edu.tw.
† Institute of Chemistry, Academia Sinica.
(4) (a) Pannell, K. H.; Rozell, J. M.; Lii, J.; Tien-Mayr, S.-Y.
Organometallics 1988, 7, 2524. (b) Berryhill, S. R.; Sharenow, B. J.
Organomet. Chem. 1981, 221, 143. (c) Pannell, K. H.; Cervantes, J.;
Parkanyi, L.; Cervantes-Lee, F. Organometallics 1990, 9, 859. (d) Thum,
G.; Ries, W.; Greissinger, D.; Malisch, W. J. Organomet. Chem. 1983,
252, C67. (e) Pannell, K. H.; Cervantes, J.; Hernandez, C.; Casslas, J.;
Vincenti, S. Organometallics 1986, 5, 1056. (f) Sharma, S.; Cervantes, J.;
Mata-Mata, J. L.; Brun, M.-C.; Cervantes-Lee, F.; Pannell, K. H. Orga-
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Dalton. Ttrans. 2003, 3727. (b) Metal Clusters in Chemistry; Braunstein,
P., Oro, L. A., Raithby, P. R., Eds.; Wiley, VCH, 1999. (c) Hidai, M.;
Orsaku, M.; Ue, M.; Koyasu, Y.; Kodama, T.; Uchida, Y. Organometallics
1983, 2, 292.
‡ Department of Chemistry, National Central University.
§ Institute of Bioscience and Biotechnology, National Taiwan Ocean
University.
(1) (a) Band, E.; Muetterties, E. L. Chem. ReV. 1978, 78, 639. (b) Shriver,
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1999, 18, 3116. (e) Siegel, J. S.; Baldridge, K. K.; Linden, A.; Dorta, R.
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10.1021/om800789m CCC: $40.75
2009 American Chemical Society
Publication on Web 11/26/2008

Single Thiolato-Bridged Heterodinuclear Complexes
Organometallics, Vol. 28, No. 1, 2009 265
Scheme 1
biological activities are concerned.14 Many of them are bimetal-
lic complexes.14a14c The common source of the thiolate ligands
in the synthesis of thiolato complexes with M-SR bonding is
organic sulfides such as RSH and RSSR.15 In addition, metal-
lothiolate can transfer thiolate ligand to another metal center
and is also used as a thiolate ligand source in the synthesis of
thiolato complexes.16 A vast number of bimetallic compounds
containing (µ-SR)2 bridges were reported.17 Because only a
small number of heterobimetallic compounds with a single
(µ-SR) bridge have been synthesized, the synthesis of such
complexes becomes more challenging in chemistry.18
In continuation of our studies in heterobimetalic complexes,16,19
this article reports the synthesis and characterization of two less
common single-thiolato-bridged heterobimetallic complexes,
Cp(CO)2W(µ-SPh)(µ-Cl)Ru(CO)(Cl)(PPh3) (1) and Cp(CO)-
(Cl)W(µ-SPh)(µ-Cl)Ru (CO)2(PPh3) (2), and a novel intramo-
lecular exchange of carbonyl and chloride ligands between
different metal centers (W and Ru) in the conversion of 1 to 2.
(10) (a) Bunnet, J. F. Acc. Chem. Res. 1972, 5, 139. (b) Sauter, F.;
Frohlich, H.; Kalt, W. Synthesis 1989, 771. (c) Frohlich, H.; Kalt, W. J.
Org. Chem. 1990, 55, 2993. (d) Nelson, D. J.; Sager, S. H. Heteroat. Chem.
1998, 9, 623. (e) Piers, E.; Brown, R. K. Can. J. Chem. 1963, 41, 329. (f)
Eaborn, C.; Lickiss, P. D.; Najim, S. T. J. Chem. Soc., Perkin Trans. 1993,
391. (g) Pietri, N.; Monnier, M.; Aycard, J.-P. J. Org. Chem. 1998, 63,
2462. (h) Koch, R.; Wang, M. W.; Wentrup, C. J. Org. Chem. 1996, 51,
6809. (i) Popkova, V. Y.; Anisimov, V. M.; Dolenko, G. N.; Semenenko,
M. N.; Fedoseev, V. M. J. Chem. Soc., Perkin Trans. 1995, 1375.
(11) Miller, R. E.; Guengerich, F. P. Biochemistry 1982, 21, 1090.
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tallics 1986, 5, 1929. (b) Balch, A. L.; Fossett, L. A.; Olmstead, M. M., Jr.
Organometallics 1988, 7, 430. (c) Balch, A. L.; Fossett, L. A.; Guimerans,
R. R.; Olmstead, M. M.; Reedy Jr, P. E.; Wood, F. E. Inorg. Chem. 1986,
25, 1248. (d) Balch, A. L.; Fossett, L. A.; Guimerans, R. R.; Olmstead,
M. M., Jr. Inorg. Chem. 1986, 25, 1397.
Results and Discussion
Synthesis and Characterization of 1. When a dichlo-
romethane solution of CpW(CO)3SPh and RuCl2(PPh3)3 was
stirred at room temperature for 12 h, the heterodinuclear
compound Cp(CO)2W(µ-SPh)(µ-Cl)Ru(CO)(Cl)(PPh3) (1) was
formed in high yield (Scheme 1).
Compound 1 is a 34e heterodinuclear metal-metal bonded
compound with a thiolato and a chloride bridge (Figure 1) and
is stable both as a solid and in solution. Its structure was
characterized by single-crystal X-ray diffraction analysis.
Absorption peaks at 2010 and 1954 cm-1 in the IR spectrum
of 1 are assigned to the ν(Ct O) bands of the two terminal
carbonyls on W based on the comparison with that of W-CO
(2031, 1938 cm-1) of CpW(CO)3SPh.20 The Ru-CO absorption
(13) Esswein, A. J.; Veige, A. S.; Nocera, D. G. J. Am. Chem. Soc.
2005, 127, 16641.
(14) (a) Sokpa, E. I. K.; Calfee, D. T.; Allred, B. R. T.; Davis, J. L.;
Haub, E. K.; Rich, A. K.; Porter, A.; Mashuta, M. S.; Richardson, J. F.;
Noble, M. E. Inorg. Chem. 1999, 38, 802. (b) DuBois, M. R. Chem. ReV.
1989, 89, 1. (c) Garcia, J. J.; Mann, B. E.; Adams, N. A.; Bailey, N. A.;
Maitlis, P. J. Am. Chem. Soc. 1995, 117, 2179. (d) Nishibayash, Y.; Wakiji,
I.; Hidia, M. J. Am. Chem. Soc. 2000, 122, 11019. (e) Qu, J.-P.; Masui, D.;
Ishii, Y.; Hidia, M. Chem. Lett. 1998, 1003. (f) Nishibayash, Y.; Yamanashi,
M.; Wakiji, I.; Hidia, M. Angew. Chem., Int. Ed. 2000, 39, 2909. (g) Takagi,
Y.; Matsuzaka, H.; Ishii, Y.; Hidia, M. Organometallics 1997, 16, 4445.
(15) (a) Ahmed, M.; Bruce, R.; Knox, G. R. J. Organomet. Chem. 1966,
6, 1. (b) Brandenburg, K. L.; Heeg, M. J.; Abrahamson, H. B. Inorg. Chem.
1987, 26, 1064. (c) Lang, R. F.; Ju, T. D.; Kiss, G.; Hoff, C. D.; Bryan,
J. C.; Kubas, G. J. J. Am. Chem. Soc. 1994, 116, 7917. (d) Abrahamson,
H. B.; Marxen, H. Organometallics 1993, 12, 2835.
(18) Guerchais, J. E.; LeQuere, J. L.; Petillon, F. Y.; Muir, Lj. M.; Muir,
K. W.; Sharp, D. W. A. J. Chem. Soc., Dalton. Ttrans. 1982, 283. (b) Ehrl,
W.; Vahrenkamp, H. Chem. Ber. 1972, 105, 1471. (c) Uson, R.; Uson,
M. A.; Herrero, S.; Rello, L. Inorg. Chem. 1998, 37, 4473.
(19) (a) Hossain, Md. M.; Lin, H.-M.; Zhu, J.; Lin, Z.; Shyu, S.-G.
Organometallics 2006, 25, 440. (b) Hossain, Md. M.; Lin, H.-M.; Shyu,
S.-G. Organometallics 2004, 23, 3941. (d) Hossain, Md. M.; Lin, H.-M.;
Shyu, S.-G. Eur. J. Inorg. Chem. 2001, 2655. (e) Shyu, S.-G.; Hsu, J.-Y.;
Lin, P.-J.; Wu, W.-J.; Peng, S.-M.; Lee, G.-H.; Wen, Y.-S. Organometallics
1994, 13, 1699.
(16) Hossain, Md. M.; Lin, H.-M.; Shyu, S.-G. Organometallics 2003,
22, 3262, and reference therein.
(17) (a) Stephan, D. W.; Nadaski, T. T. Coord. Chem. ReV. 1996, 147,
147. (b) Blower, P. J.; Dilwarth, J. R. Coord. Chem. ReV. 1987, 121, 121.
(20) Weinmann, D. J.; Abrahamson, H. B. Inorg. Chem. 1987, 26, 2133.

266 Organometallics, Vol. 28, No. 1, 2009
Hossain et al.
cm-1 in the IR spectrum of 1 could be the superposition of one
of the W-CO adsorption peaks and the Ru-CO adsorption
peak.
During the formation of 1, one of the carbonyl ligands on
the W site in CpW(CO)3SPh migrates onto the Ru site. It may
not be a scrambling reaction because 1 is formed in high yield
(93%). Although formal oxidation states of W and Ru in
CpW(CO)3SPh, RuCl2(PPh3)3, and 1 are both +2, the migration
of the carbonyl ligand is possibly electronic in nature. A possible
pathway for the formation of 1 is shown in Scheme 1.
RuCl2(PPh3)3 is a 16e complex and therefore is a coordina-
tively unsaturated species. The metallothiolate CpW(CO)3SPh
can coordinate to the Ru in RuCl2(PPh3)3 through a lone pair
of electrons on the sulfur atom to form a non-metal-metal-
bonded 36e dimer, CpW(CO)3(µ-SPh)RuCl2(PPh3)3, with a
µ-SPh bridge. A dative metal-metal bond from W to Ru may
replace a bulky PPh3 ligand on Ru, forming the 34e complex
CpW(CO)3(µ-SPh)RuCl2(PPh3)2 (denoted as A) to release the
steric hindrance and brings the two metals closer. Through the
formation of the dative metal-metal bonding, the Ru in A
becomes electron rich, and the electron density on W is reduced.
This difference in electron density drives the migration of the
π-acceptor carbonyl ligand from the electron-deficient W atom22
to the electron-rich Ru atom22,23b to substitute a weak π-acceptor
triphenylphosphine ligand through the formation of the bridging
chloride to redistribute the electron density of the metals to form
1.
Figure 1. ORTEP drawing of 1, with 30% thermal ellipsoids.
Hydrogen atoms are omitted.
The reaction of CpW(CO)3SPh and RuCl2(PPh3)4 under
identical conditions also afforded 1 in high yield because
triphenylphosphine ligands in both RuCl2(PPh3)4 and
RuCl2(PPh3)3 are labile. Production of the similar intermediate
24
RuCl2(PPh3)2(solvent)2 for both complexes in solvents with
weak coordination abilities has been reported.
Thermolysis of 1. After heating at 80 °C, the color of the
toluene solution of 1 changed from violet to yellow. Compound
2, an orange solid, was obtained after chromatography.
The elemental analysis of 2 is similar to that of 1. This implies
that compound 2 has the same empirical formula of 1. The room-
temperature 31P{1H} and 1H NMR spectra of 2 show two peaks
for the triphenylphosphine and the cyclopentadiene ring,
respectively, and do not contain signals corresponding to 1. No
JP-W satellites are observed in the 31P{1H} NMR spectrum,
showing that the triphenylphosphine ligand is coordinated to
Ru. IR of 2 shows three terminal CO absorption peaks,
indicating no bridging CO is present, and the pattern of the
spectra (both the number of peaks and their positions) is different
from that of 1. All this implies that two isomers (denoted 2a
and 2b) are present in 2, and compounds 1 and 2 are
constitutional isomers.
1
The variable-temperature 31P{1H} and H NMR spectra of
the compounds indicate that the isomers do not convert to each
other in the variable-temperature range of the experiment (65
to -68 °C) because the ratios of the intensities of triph-
enylphosphine and cyclopentadiene signals are similar as a
function of temperature.25
Figure 2. (a) ORTEP drawing of 2a, with 30% thermal ellipsoids.
Hydrogen atoms are omitted. (b) ORTEP drawing of 2b, with 30%
thermal ellipsoids. Hydrogen atoms are omitted.
(22) (a) Shima, T.; Ito, J.-I.; Suzuki, H. Organometallics 2001, 20, 10.
(b) Ohki, Y.; Matsuura, N.; Marumoto, T.; Kawaguchi, H.; Tatsumi, K.
J. Am. Chem. Soc. 2003, 125, 7978.
(23) (a) Meiere, S. H.; Keane, J. M.; Gunnoe, T. B.; Sabat, M.; Harman,
W. D. J. Am. Chem. Soc. 2003, 125, 2024. (b) Matsuo, Y.; Kuninobu, Y.;
Ito, S.; Nakamura, E. Chem. Lett. 2004, 33, 68.
should be around 1950 cm-1 based on the comparison with the
ν(Ct O) bands of Ru-CO (1948, 1955 cm-1) of (CO)(PPh3)-
Ru(µ-Cl)(µ-SPh)2Ru(CO)(PPh3)2,21 and the broad peak at 1954
(24) Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28,
945.
(25) Cholli, A. L.; Lau, M. L. Appl. Spectrosc. 1993, 47, 357.
(21) Kuznik, N.; Krompice, S.; Bieg, T.; Baj, S.; Skutil, K.; Chrobok,
A. J. Organomet. Chem. 2003, 665, 167.

Single Thiolato-Bridged Heterodinuclear Complexes
Organometallics, Vol. 28, No. 1, 2009 267
Chart 1
Separation of 2a and 2b failed. However, two different types
of single crystals of 2 for single-crystal X-ray diffraction analysis
were obtained from the same batch of compound 2 by ether
diffusion into a dichloromethane solution of 2 at different
temperatures. Violet single crystals of 2a and 2b were obtained
at -4 and -15 °C, respectively, from two sets of crystal growth
experiments from the same batch of 2. The molecular structures
of 2a and 2b are shown in Figure 2a and b, respectively. Two
independent molecules of 2a were crystallized in the asymmetric
unit cell.
Both 2a and 2b are 34e heterodinuclear metal-metal bonded
compounds with a thiolato and a chloride bridge (Figure 2a and
b). The only difference in their structures is the orientation of
the lone pair of electrons and the phenyl group on the sulfur
atom of the thiolato bridge with respect to the folded RuSClW
core. In 2a, the phenyl group on sulfur points away from the
bridging Cl of the folded RuSClW core. In 2b, the orientations
of the phenyl group and the lone pair of electrons on sulfur are
opposite that of 2a, with the phenyl group pointing toward and
the lone pair of electrons pointing away from the bridging Cl.
Thus 2a and 2b are stereoisomers.
respectively, to form 2, and the environments of the other ligands
are kept identical with that of 1 (Figure 2a and b). Ligand
migrations in organometallic complexes are common and occur
in both intermolecular and intramolecular pathways.3-8,28
Isomerization of 1 to 2 is irreversible and is proposed to be
intramolecular in nature because the conversion of 1 to 2 is
almost quantitative without any byproducts. In addition, ther-
molysis of 1 under 13CO resulted in the decomposition of 1
before isomerization and no compound 2 was obtained. Complex
CpW(CO)3Cl is observed in the decomposition product. This
observation further indirectly excludes the intermolecular
isomerization process through external CO from W-CO bond
breaking to form the Ru-CO bond in 2. The external CO-
induced transfer reaction of a silyl group in the phosphido-
bridged bimetallic Fe-Pt system has been observed.28 In
addition, bridge/terminal halide exchange and bridge/terminal
carbonyl exchange in trinuclear complexes were reported (Chart
1).12 However, to the best of our knowledge, the internal mutual
carbonyl-chloride migration between heteroatoms (W and Ru)
in 1 to form 2 has not been observed previously.
In 1, both chloride and carbonyl ligands have bridging ability.
Considering the flexibility of carbonyl and chloride ligands
toward terminal/bridging mode, we suggest that the 34e dimer
B (Scheme 1) is the intermediate during the isomerization of 1
to 2.
Two absorption peaks at 2033 and 1971 cm-1 in the IR
spectrum of 2 are assigned to the ν(Ct O) bands of the two
terminal carbonyls on Ru based on the comparison with that of
the Ru-CO (2016, 2079, and 1951 cm-1) in [Ru(CO)2(PPh3)(µ-
SPh)]2.26 The third absorption peak at 1887 cm-1 is assigned
to the ν(Ct O) band of the carbonyl on W based on the
comparison with that of the W-CO (1881 cm-1) in Cp(CO)-
(Cl)W(µ-CMe)(µ-Cl)Ru (CO)(PPh3)2.27 Broad peaks at 1972
and 1887 cm-1 may be due to the superposition of the signals
of the two isomers in the sample.
The Ru atom in 1 is electron rich because of the dative W-Ru
bonding and the electron-donating phosphine ligand. Donation
of an electron from the Ru metal to the π* of CO on W to
form the bridging carbonyl to form the 34e dimer B can reduce
the electron density on Ru (Scheme 1). The terminal chloride
ligand on Ru in B can coordinate to the adjacent W to form a
bridging chloride and pushes the bridging carbonyl to Ru to
accomplish the CO migration. The original bridging chloride
ligand completes the chloride migration by converting itself to
a W terminal Cl to form 2. Although we are not able to isolate
any intermediate, similar bonding modes of CO and Cl in the
proposed intermediate B (Scheme 1) were structurally estab-
lished in [Rh2(Ph2PCH2PPh2)2(µ-Cl)(µ-CO)(CO)2]+,29a [Re2(Ph2-
PCH2PPh2)2(µ-Cl)(µ-CO)(CO)Cl2(EtCN)]+,29b and (CO)3Mo(µ-
Cl)(µ-CO)(Ph2PCH2PPh2)Rh(NBD).29c
In the thermolysis of 1, one CO on W and the terminal Cl
on Ru in 1 are replaced by a terminal Cl and a terminal CO,
(26) Shiu, K.-B.; Wang, S.-L.; Liao, F.-L.; Chiang, M. Y.; Peng, S.-
M.; Lee, G.-H.; Wang, J.-C.; Liou, L.-S. Organometallics 1998, 17, 1790.
(27) Howard, J. A. K.; Laurie, J. C. V.; Stone, F. G. A. J. Chem. Soc.,
Dalton. Trans. 1985, 2017.
(28) (a) Braunstein, P.; Knorr, M.; Hirle, B.; Reinhard, G.; Schubert,
U. Angew. Chem., Int. Ed. Engl. 1992, 31, 1583. (b) Braunstein, P.; Faure,
T.; Knorr, M. Organometallics 1999, 18, 1791.
(29) (a) Cowie, M. Inorg. Chem. 1979, 18, 286. (b) Cotton, F. A.;
Dunbar, K. R.; Falvello, L. R.; Walton, R. A. Inorg. Chem. 1985, 24, 4180.
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Chem. 1991, 410, 101.
The redistribution of electron density in the isomerization of
1 to 2 is revealed by the frequency change of CO absorption
peaks in their IR spectra. The lower stretching frequency (1887

268 Organometallics, Vol. 28, No. 1, 2009
Hossain et al.
Table 1. Selected Bond Lengths (Å) and Bond Angles (deg) for 1,
2a, and 2b
These complexes have a similar core structure: one chloride
bridge, one thiolato bridge, and a metal-metal bond between
the metals. The W1-Ru1 bond distances in 1, 2a, and 2b are
2.8394(9), 2.7481(av), and 2.7657(3) Å, respectively, and are
well in accord with the literature values.30 These bond distances
are varied according to the variation of their respective acute
angles W-S-Ru (71.54(6)°, 68.64 (av)°, and 68.89(2)°) and
W-Cl-Ru (70.06(6)°, 68.06(av)°, and 68.328 (19)°). The
W1-Ru1 distance (2.8394(9) Å) is comparatively long and is
consistent with the dative bonding character. The W1-Ru1 bond
distances in 2a and 2b are 0.1 Å shorter than that in 1, implying
that metal-metal bonds in 2a and 2b are comparatively
covalent.
The Cl(1)-W(1)-Ru(1)-S(1) dihedral angles are 96.03(9)°,
93.21(6)°, and 102.33(3)° in 1, 2a, and 2b, respectively. A
bigger dihedral angle in 2b than in 2a reflects a larger steric
hindrance between the phenyl group on the bridging sulfur atom
and the bridging chloride. In 2b, the phenyl group points to the
center of the SWRuCl core. In 2a, the phenyl group points in
the opposition direction and has a smaller interaction with the
bridging chloride. The SWRuCl core structures of 1 and 2a are
similar, with the phenyl group on the sulfur pointing away from
the center of the core.
bonds
1
2a
2b
W1-S1
2.488(2)
1.993(10)
1.999(9)
2.481(2)
2.4720(14)
1.979(7)
2.4846(7)
1.950(3)
W1-C1
W1-C2
W1-C11
2.4862(15)
2.4905(15)
2.253(6)
2.291(6)
2.381(6)
2.363(6)
2.285(6)
2.3921(16)
2.4316(15)
2.4734(7)
2.4857(8)
2.276(3)
2.238(3)
2.289(3)
2.387(4)
2.368(3)
2.4038(8)
2.4514(7)
W1-C12
W1-C6
2.268(9)
2.338(10)
2.380(9)
2.289((9)
2.270(9)
2.366(2)
2.466(2)
2.401(2)
2.314(2)
W1-C7
W1-C8
W1-C9
W1-C10
Ru1-S1
Ru1-Cl1
Ru1-Cl2
Ru1-P1
2.3847(16)
1.896(7)
1.855(7)
1.800(6)
2.3981(7)
1.905(3)
1.843(3)
1.800(3)
Ru1-C2
Ru1-C3
1.818(8)
1.793(8)
C11-S1
angles
W1-S1-Ru1
W1-Cl1-Ru1
S1-W1-Cl1
S1-W1-C1
S1-W1-C2
S1-W1-Ru1
S1-W1- Cl2
C1-W1-C2
C1-W1-Cl1
C1-W1-Ru1
C1-W1-Cl2
C2-W1-Cl1
C2-W1-Ru1
Cl1-W1-Ru1
Cl1-W1-Cl2
Cl2-W1-Ru1
S1-Ru1-P1
S1-Ru1-Cl1
S1-Ru1-Cl2
S1-Ru1-C2
S1-Ru1-C3
S1-Ru1-W1
P1-Ru1-Cl1
P1-Ru1-Cl2
P1-Ru1-C2
71.54(6)
70.06(6)
73.38(7)
82.3(2)
130.1(3)
52.22(5)
68.89(4)
68.05(4)
72.65(5)
91.24(16)
68.89(2)
68.328(19)
79.09(2)
83.19(2)
54.18(4)
140.39(5)
54.176(17)
143.55(3)
The average bond distances of Ru1-P1 (2.3914 Å) and
Ru-C (1.8747 Å) in 2 are longer than that of Ru1-P1 (2.314(2)
Å) and Ru1-C3 (1.818(8) Å) in 1. This implies that back-
donation of electrons from Ru to these ligands is reduced in 2.
This is consistent with the IR data observed.
76.8(3)
131.9(2)
77.5(2)
131.21(18)
77.93(17)
83.77(17)
128.25(9)
74.77(9)
87.37(9)
88.0(3)
79.0(3)
54.73(5)
55.03(3)
81.38(5)
86.47(4)
103.05(5)
75.02(5)
55.460(17)
79.49(3)
89.38(2)
109.77(3)
81.10(3)
Conclusions
This paper describes the synthesis of single thiolato-bridged
heterodinulear W-Ru complexes 1 and 2 in high yield. During
thermolysis of 1 in toluene, isomerization of 1 to 2 occurred
via chloride and carbonyl ligand migration. The migration of
the carbonyl and chloride ligands in the conversion of
CpW(CO)3SPh + RuCl2(PPh3)x (x ) 3 and 4) f 1 f 2 is
stepwise. Heterobimetallic complexes with early and late
transition metals are effective as Lewis acid and Lewis base
pairs in catalytic reactions.31 Isomerization of 1 to 2 indicates
a possibility that the Lewis acidity and Lewis basicity of the
metals can be altered by the mutual redistribution of the
π-acceptor and σ-donor ligands among the metals during their
reactions.
97.86(7)
75.79(8)
160.96(8)
161.45(19)
95.07(18)
56.93(4)
158.26(9)
89.16(9)
56.936(18)
101.60(3)
103.0(2)
56.24(5)
101.89(8)
97.17(8)
98.96(5)
94.29(19)
91.97(9)
cm-1) of carbonyl on W in 2 than that in 1 (2010 and 1954
cm-1) indicates a stronger back-donation from W to carbonyl
in 2. Consistently, the stretching frequencies of Ru carbonyl
ligands in 2 (2033 and 1972 cm-1) are higher than that in 1
(1954 cm-1), indicating a weaker back-donation from Ru to its
carbonyl ligands in 2. This is because the number of π-acceptor
carbonyl ligands on the Ru center and W center has been
changed from one in 1 to two in 2 and from two in 1 to one in
2, respectively.
Experimental Section
General Procedures. All reactions and other manipulations were
performed under an atmosphere of nitrogen using standard Schlenk
Scrambling of Cl and CO between different metals was
(30) (a) Mashima, K.; Mikami, A.; Nakamura, A. Chem. Lett. 1992,
1795. (b) Shiu, K.-B.; Wang, S.-L.; Liao, F.-L.; Chiang, M. Y.; Peng, S.-
M.; Lee, G.-H.; Wang, J.-C.; Liou, L.-S. Organometallics 1998, 17, 1790.
(c) Nishibayashi, Y.; Imajima, H.; Onodera, G.; Inada, Y.; Hidia, M.;
Uemura, S. Organometallics 2004, 23, 5100. (d) Shacht, H.; Haltiwanger,
R. C.; DuBois, M. R. Inorg. Chem. 1992, 31, 1728. (e) Dev, S.; Imagawa,
K.; Mizobe, Y.; Cheng, G.; Wakatsuki, Y.; Yamazaki, H.; Hidia, M.
Organometallics 1989, 8, 1232. (f) Kondo, T.; Uenoyama, S.-Y.; Fujita,
K.-I.; Mitsudo, T.-A. J. Am. Chem. Soc. 1999, 121, 482. (g) Hankin, D. M.;
Danopoulos, A. A.; Wilkinson, G.; Sweet, T. K. N.; Hurshouse, M. B.
J. Chem. Soc., Dalton. Trans. 1996, 4063. (h) Lukas, C. R.; Newlands, M,
J.; Gabe, E. J.; Lee, F. L. Can. J. Chem. 1987, 65, 898. (i) Zhuang, B.;
Sun, H.; Pan, G.; He, L.; Wei, Q.; Zhou, Z.; Peng, S.; Wu, K. J. Organomet.
Chem. 2001, 640, 127. (j) Canich, J. A. M.; Cotton, F. A.; Dunbar, K. R.;
Falvello, L. R. Inorg. Chem. 1988, 27, 804. (k) Darensbourg, D.; Sanchez,
K. M.; Reibenspies, J. Inorg. Chem. 1988, 27, 3636. (l) Bitterwolf, T. E.;
Saygh, A. A.; Shade, J. E.; Rheingold, A. L.; Yap, G. P. A.; Lable-Sands,
L. M. Inorg. Chim. Acta 2000, 800, 300–302.
reported in the synthesis of Cp(CO)(Cl)W(µ-CMe)(µ-Cl)Ru
(CO)(PPh3)2 by the reaction between CpW(CO)2CMe and
RuCl2(PPh3)3. Chloride and carbonyl migrations between W and
Ru were proposed in the reaction; however no intermediate was
observed.27 The synthesis of 1 and the conversion of 1 to 2 in
this report provide a stepwise and almost quantitative reaction
path of the migration of carbonyl ligands from the W to Ru
site and chloride ligand from the Ru to W site in the formation
of 2 from CpW(CO)3SPh and RuCl2(PPh3)x (x ) 3 and 4).
X-ray Structures of 1, 2a, and 2b. The structures of
compounds 1, 2a, and 2b were determined by X-ray diffraction
analysis. The ORTEP drawings of 1, 2a, and 2b are shown in
Figures 1b, 2a, and 2b, respectively. Selected bond distances
and bond angles are listed in Table 1.
(31) Wheatly, N.; Kalk, P. Chem. ReV. 1999, 99, 3379.

Single Thiolato-Bridged Heterodinuclear Complexes
Organometallics, Vol. 28, No. 1, 2009 269
Table 2. Summary of Crystal Data for 1, 2a, and 2b
1
2a
2b
formula
fw
space group
a [Å]
b [Å]
c [Å]
R [deg]
[deg]
γ [deg]
V [Å3]
F(calcd) [Mg m-3
Z
C32H25O3Cl2PSWRu
876.37
P21/c
10.634(18)
19.703(4)
14.856(3)
C129H100O12Cl10P4S4W4Ru4
3588.39
P21/c
23.134(7)
14.8948(4)
C32H25O3Cl2PSWRu
876.37
P1
j
10.3393(4)
10.4859(4)
16.1041(9)
93.722(2)
101.160(2)
115.6210(10)
1522.56(12)
1.912
18.7904(5)
103.46(3)
103.8290(10)
3027.2(10)
1.923
4
6287.1(3)
1.896
2
]
2
cryst dimens [mm]
temp [K]
0.31 × 0.16 × 0.13
0.16 × 0.14 × 0.14
0.15 × 0.1 × 0.07
293(2)
293(2)
296(2)
λ(Mo KR) [Å]
2θ range [deg]
scan type
no. of reflns
no. of obsd reflns
no. of params refined
R
0.71073
50.0
ω
5618
5314 (>2.0σ(I))
365
0.0369
0.71073
50.0
ω
41 281
11 098 (>2.5σ(I))
757
0.0362
0.71073
50.0
ω
22 333
6918 (>2.5σ(I))
370
0.0232
Rw
0.0884
0.0747
0.0513
GoF
0.981
-1.631, 1.326
1.062
-1.340, 1.340
0.986
-0.376, 1.045
Dmap min., max. [e/Å3]
1
techniques. Commercially available chemicals were purchased and
used without further purification. All solvents were dried with Na
and benzophenone under N2 and distilled immediately prior to use.
Compounds CpW(CO)3SPh and RuCl2(PPh3)x (x ) 3 and 4) were
prepared following reported procedures.32 The 1H and 31P{1H}
NMR spectra were recorded using a Bruker Ac-300 spectrometer.
Variable-temperature 1H and 31P{1H} NMR spectra were recorded
using a Bruker DRX500/AV400 spectrometer. The 31P{1H} shifts
are referenced to 85% H3PO4. Microanalyses were performed by
use of a Perkin-Elmer 2400 CHN analyzer.
mixture was monitored by 31P{1H} and H NMR. Compound 1
was decomposed to CpW(CO)3Cl33 with trace amounts of other
compounds. No isomerization of 1 to 2 was observed.
Crystal Structure Determination of 1, 2a, and 2b. Single
crystals of 1 for X-ray diffraction analysis were grown by slow
evaporation of dichloromethane solution layered by hexane at -4
°C. Single crystals of 2a and 2b were grown from two sets of crystal
growth experiments by ether diffusion into a dichloromethane
solution of 2 at -4 and -15 °C, respectively, from the same batch
of 2. The crystals of 1, 2a, and 2b were mounted on a glass fiber
for data collection, and the data of 1, 2a, and 2b were collected by
using Mo KR radiation at CCD. Detailed data collection parameters
are given in Table 2. Data collections were carried out by Mo KR
radiation (λ ) 0.71073 Å) on a Bruker X8 Apex CCD at room
temperature. The unit-cell parameters were obtained by least-squares
fit to the automatically centered settings for reflections on a Bruker
X8 Apex CCD diffractometer. Intensity data were collected by using
the ω/2θ scan mode. The structures were solved by direct methods
(SHELX-97). All non-hydrogen atoms were located from the
difference Fourier maps and were refined by full-matrix least-
squares procedures. Hydrogen atoms were included in idealized
positions but not refined. Calculations and full-matrix least-squares
refinements were performed utilizing the WINGX program package.
Synthesis of 1. Dichloromethane (50 mL) was added to a solid
mixture of CpW(CO)3SPh (100 mg, 0.226 mmol) and RuCl2(PPh3)3
(216 mg, 0.226 mmol), and the solution was stirred for 12 h at
room temperature. The solution was concentrated, and a brown
precipitate was obtained by adding hexane. After separation by
filtration, the residue was dissolved in dichloromethane (5 mL) and
was chromatographed on silica gel using dichloromethane as an
eluent. Compound 1 was obtained as a violet solid from the violet
band after removing the solvent. Yield: 184 mg, 93%. Anal. Calcd
for C32H25O3PSCl2WRu: C, 43.82; H, 2.85. Found: C, 43.52, H,
1
3.11. IR (CH2Cl2): ν(CO) 2009 (s), 1954 (vs, br) cm-1. H NMR
(CDCl3): δ 7.73-6.78 (m, 20H, C6H5), 5.69 (s, 5H, C5H5). 31P{1H}
NMR (CH2Cl2): δ 57.87 (s). Reaction between CpW(CO)3SPh (50
mg, 0.113 mmol) and RuCl2(PPh3)4 (138 mg, 0.113 mmol) in
dichloromethane (30 mL) under similar reaction conditions afforded
1 in 91% yield (89 mg).
Acknowledgment. We acknowledge the National Science
Council, ROC, Department of Industrial Technology, Min-
istry of Economic Affairs, ROC (grant no. 97-EC-17-A-08-
R7-0706), and Academia Sinica for financial support of this
work.
Thermolysis of 1. A toluene solution (30 mL) of 1 (100 mg,
0.114 mmol) was heated at 80 °C for 3 h. The color of the solution
changed from violet to yellow. The solvent was removed, and the
residue was dissolved in dichloromethane (5 mL). After chroma-
tography on silica gel using dichloromethane/hexane (4:1) as the
eluent, compound 2 was obtained with 96% yields (96 mg). Anal.
Calcd for C32H25O3PSCl2WRu: C, 43.82; H, 2.85. Found: C, 43.49,
H, 3.25. IR (CH2Cl2): ν(CO) 2033 (vs), 1972 (vs, br), 1887 (m, br)
Supporting Information Available: Tables of atomic coordi-
nates, isotropic and anisotropic displacement parameters, and all
bond distances and angles; experimental details of the X-ray studies
for 1, 2a, and 2b; variable-temperature spectra of 31P{1H} and H
1
1
cm-1. H NMR (CDCl3): δ 7.47-6.78 (m, 20H, C6H5), 5.49 (s,
NMR. This material is available free of charge via the Internet at
5H, C5H5), 5.44 (s, 5H, C5H5). 31P{1H} NMR (CH2Cl2): δ 46.45
(s), 44.55 (s).
http://pubs.acs.org.
Thermolysis of 1 in the Presence of 13CO. A toluene solution
(10 mL) of 1 (50 mg, 0.057 mmol) was degassed by freeze-thaw
method and was heated at 80 °C for 3 h under 13CO. The reaction
OM800789M
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