Synthesis and reactions of five-coordinate mono- and binuclear thiocarbonyl - alkenyl and thioacyl complexes of ruthenium(II)

Article abstract of DOI:10.1021/om700518m

The reactions of [RuHCl(CS)(PPh₃)₃] with R ¹C≡CR² (R¹ = R² = H, Ph, CO₂Me; R¹ = H, R² = C₆H ₄Me-4; R¹ = C≡CPh, R² = Ph) lead to the five- or six-coordinate (R¹ = R² = CO₂Me) σ-alkenyl complexes [Ru(CR¹=CHR²)Cl(CS)(PPh ₃)₂], the stilbenyl derivative being also formed by thermolysis of [RuCl(κ²-O₂CH)(CS)(PPh ₃)₂j in the presence of diphenylacetylene. These complexes rapidly react with carbon monoxide to provide the bidentate thioacyl complexes [Ru(η²-SCCR¹=CHR²)Cl(CO)(PPh ₃)₂] (R¹ = R² = H, Ph; R¹ = H, R² = Ph; R¹ = C≡CPh, R₂ = Ph) or the σ-alkenyl tautomer [Ru(CR¹= CHR²)Cl(CO)(CS) (PPh₃)₂] (R¹ = R² = CO ₂Me), depending on the alkenyl substituent. The compound [RuHCl(CS)(PPh₃)₃] reacts with 1/2 equiv of 1,4-diethynylbenzene to provide the coordinatively unsaturated bimetallic species [(Ph₃P)₂(SC)ClRu(CH=CHC₆H ₄CH=CH)RuCl(CS)(PPh₃)₂] in situ, which undergoes migratory insertion on addition of carbon monoxide to give the bis(thioacyl) species [(Ph₃P)₂(OC)ClRu-(η²- SCCH=CHC₆H₄CH=CHCS-η²)RuCl(CO)(PPh ₃)₂]. On reaction with BSD (2,1,3-benzoselenadiazole), [Ru(CH=CH₂)Cl(CS)(PPh₃)₂] gives [Ru(CH=CH ₂)Cl(CS)(BSD)(PPh₃)₂] without migration of the alkenyl group. The complex [RuHCl(CS)(BSD)(PPh₃)₂] results from the reaction of [RuHCl(CS)(PPh₃)₃] and BSD, and this complex hydroruthenates alkynes cleanly to provide [Ru(CR¹=CHR ²)Cl(CS)(BSD)(PPh₃)₂], carbonylation of which leads to loss of BSD and formation of [Ru(η²-SCCR ¹=CHR²)Cl(CO)(PPh₃)₂]. Addition of carboxylate donors R′CO₂_ (R′ = H, Fc) to the complexes [RuRCl(CS)(PPh₃)₂] (R = CH=CH₂, C(C≡CPh)=CHPh) results in the complexes [RuR(κ²-O ₂CR′)(CS)(PPh₃)₂], without migratory insertion. A trimetallic example, Fe[C₅H₄CO ₂Ru{C(C≡CPh)=CHPh}(CS)(PPh₃)₂] ₂, was formed in the corresponding reaction with 1,1′- ferrocenedicarboxylic acid and Et₃N. The crystal structures of the complexes [Ru(CPh=CHPh)Cl(CS)(PPh₃)₂], [Ru{C(C≡CPh)=CHPh}Cl(CS)(PPh₃)₂], [Ru{η²-SCC-(C≡CPh)=CHPh}Cl(CO)(PPh₃) ₂], [Ru{C(C≡CPh)=CHPh}(κ²-O ₂CFc)(CS)(PPh₃)₂] and Fe[C₅H ₄CO₂-Ru{C(C≡CPh)=CHPh}(CS)(PPh₃) ₂]₂ are reported.

Full text of DOI:10.1021/om700518m

6114
Organometallics 2007, 26, 6114-6125
Synthesis and Reactions of Five-Coordinate Mono- and Binuclear
Thiocarbonyl-Alkenyl and Thioacyl Complexes of Ruthenium(II)
Andrew R. Cowley,† Andrew L. Hector,‡ Anthony F. Hill,*,§ Andrew J. P. White,‡
David J. Williams,‡ and James D. E. T. Wilton-Ely*,†
Chemistry Research Laboratory, UniVersity of Oxford, Oxford, U.K., Department of Chemistry,
Imperial College, London, U.K., and Research School of Chemistry, Institute of AdVanced Studies,
Australian National UniVersity, Canberra, Australian Capital Territory, Australia
ReceiVed May 24, 2007
The reactions of [RuHCl(CS)(PPh3)3] with R1CtCR2 (R1 ) R2 ) H, Ph, CO2Me; R1 ) H, R2 )
C6H4Me-4; R1 ) CtCPh, R2 ) Ph) lead to the five- or six-coordinate (R1 ) R2 ) CO2Me) σ-alkenyl
complexes [Ru(CR1dCHR2)Cl(CS)(PPh3)2], the stilbenyl derivative being also formed by thermolysis
of [RuCl(κ2-O2CH)(CS)(PPh3)2] in the presence of diphenylacetylene. These complexes rapidly react
with carbon monoxide to provide the bidentate thioacyl complexes [Ru(η2-SCCR1dCHR2)Cl(CO)(PPh3)2]
(R1 ) R2 ) H, Ph; R1 ) H, R2 ) Ph; R1 ) CtCPh, R2 ) Ph) or the σ-alkenyl tautomer [Ru(CR1d
CHR2)Cl(CO)(CS)(PPh3)2] (R1 ) R2 ) CO2Me), depending on the alkenyl substituent. The compound
[RuHCl(CS)(PPh3)3] reacts with 1/2 equiv of 1,4-diethynylbenzene to provide the coordinatively unsaturated
bimetallic species [(Ph3P)2(SC)ClRu(CHdCHC6H4CHdCH)RuCl(CS)(PPh3)2] in situ, which undergoes
migratory insertion on addition of carbon monoxide to give the bis(thioacyl) species [(Ph3P)2(OC)ClRu-
(η2-SCCHdCHC6H4CHdCHCS-η2)RuCl(CO)(PPh3)2]. On reaction with BSD (2,1,3-benzoselenadiazole),
[Ru(CHdCH2)Cl(CS)(PPh3)2] gives [Ru(CHdCH2)Cl(CS)(BSD)(PPh3)2] without migration of the alkenyl
group. The complex [RuHCl(CS)(BSD)(PPh3)2] results from the reaction of [RuHCl(CS)(PPh3)3] and
BSD, and this complex hydroruthenates alkynes cleanly to provide [Ru(CR1dCHR2)Cl(CS)(BSD)(PPh3)2],
carbonylation of which leads to loss of BSD and formation of [Ru(η2-SCCR1dCHR2)Cl(CO)(PPh3)2].
-
Addition of carboxylate donors R′CO2 (R′ ) H, Fc) to the complexes [RuRCl(CS)(PPh3)2] (R )
CHdCH2, C(CtCPh)dCHPh) results in the complexes [RuR(κ2-O2CR′)(CS)(PPh3)2], without migratory
insertion. A trimetallic example, Fe[C5H4CO2Ru{C(CtCPh)dCHPh}(CS)(PPh3)2]2, was formed in the
corresponding reaction with 1,1′-ferrocenedicarboxylic acid and Et3N. The crystal structures of the
complexes [Ru(CPhdCHPh)Cl(CS)(PPh3)2], [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2], [Ru{η2-SCC-
(CtCPh)dCHPh}Cl(CO)(PPh3)2], [Ru{C(CtCPh)dCHPh}(κ2-O2CFc)(CS)(PPh3)2] and Fe[C5H4CO2-
Ru{C(CtCPh)dCHPh}(CS)(PPh3)2]2 are reported.
Scheme 1. Alkyne Hydrometalation by
[RuHCl(CO)(PPh3)2(L)] (L ) PPh3, Py,
Introduction
3,5-dimethylpyrazole, 2,1,3-benzoselenadiazole)a
There has been considerable interest in the reactions of the
complexes [RuHCl(CO)(PPh3)2(L)] (L ) PPh3, dimethylpyra-
zole, pyridine, 2,1,3-benzoselenadiazole) with alkynes, which
lead to facile hydroruthenation of the CtC triple bond and the
formation of σ-alkenyl complexes (Scheme 1).1 Similar reactiv-
ity has also been observed in the reactions of [RuHCl(CO)-
(PPh3)3] and [RuHI(CO)(NCMe)(PPh3)2] with phosphaalkynes,
leading to reactive phosphaalkenyl complexes that are precursors
to a range of unsaturated organophosphorus ligands.3
* To whom correspondence should be addressed. E-mail: a.hill@anu.edu.au
(A.F.H.), james.wilton-ely@chem.ox.ac.uk (J.D.E.T.W.-E.).
† University of Oxford.
‡ Imperial College.
§ Australian National University.
a Legend: (i) -L, + R1CtCR;2 (ii) alkyne insertion; (iii) +L
(L * PPh3).
(1) (a) Torres, M. R.; Vegas, A.; Santos, A. J. Organomet. Chem. 1986,
309, 169. (b) Romero, A.; Santos, A.; Vegas, A. Organometallics 1988, 7,
1988. (c) Torres, M. R.; Perales, A.; Loumrhari, H.; Ros, J. J. Organomet.
Chem. 1990, 385, 379. (d) Loumrhari, H.; Ros, J.; Torres, M. R.; Perales,
A. Polyhedron 1990, 9, 907. (e) Montoya, J.; Santos, A.; Echavarren, A.
M.; Ros, J. J. Organomet Chem. 1990, 390, C57. (f) Torres, M. R.; Perales,
A.; Loumrhari, H.; Ros, J. J. Organomet. Chem. 1990, 384, C61. (g) Hill,
A. F.; Melling, R. P. J. Organomet. Chem. 1990, 396, C22. (h) Loumrhari,
H.; Matas, L.; Ros, J.; Torres, M. R.; Perales, A. J. Organomet. Chem.
1991, 403, 373. (i) Hill, A. F.; Melling, R. P.; Thompsett, A. R. J.
Organomet. Chem. 1991, 402, C8. (j) Romero, A.; Santos, A.; Lo´pez, J.;
Echavarren, A. M. J. Organomet. Chem. 1990, 391, 219.
Thiocarbonyl ligands display an enhanced propensity for
entering into migratory insertion reactions, compared with the
case for carbonyl ligands. In this respect migratory insertion
reactions involving thiocarbonyls and hydride,3 aryl,4 silyl,5
boryl,6a and borane6b ligands have been demonstrated previously.
While parallels with aryl-carbonyl coupling are not surprising,
the migration reactions involving hydride, silyl, and boryl
10.1021/om700518m CCC: $37.00 © 2007 American Chemical Society
Publication on Web 11/07/2007

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6115
Chart 1. Thioacyl and Metallathiirene Canonical Forms
Scheme 2. Osmium Alkenyl-Thiocarbonyl Migratory
Insertion Reactions (L ) PPh3)a,7b,f
ligands are remarkable, given that these are not generally
observed for carbonyl ligands. Furthermore, metallacyclic
thioacyls are implicitly or directly observed in the coupling of
alkynes with thiocarbonyl ligands en route to metallacyclobute-
nethiones, metallabenzenes, or cyclopentadienethione com-
plexes.7 This facility may be traced to the π-acceptor orbitals
of free CS being of lower energy than those for CO. However,
given that the majority of these observed reactions have involved
divalent (“soft”) ruthenium or osmium complexes that convert
to bidentate thioacyls (metallathiirenes, C; Chart 1),9 the strength
of the resulting M-S (M ) Ru, Os) bond presumably
contributes a thermodynamic impetus for the process.
Migratory insertion reactions involving alkenyl and thiocar-
bonyl ligands remain rare,7b,f,9 primarily due to the lack of
suitable substrates bearing both these ligands. The osmium
complex [Os(CPhdCHPh)Cl(CS)(PPh3)2] results from the ad-
dition of hydrogen chloride to the zerovalent tolane complex
[Os(CS)(PhCtCPh)(PPh3)2] and undergoes CO-promoted mi-
gratory insertion.7b However, the synthesis of the precursor
alkyne complex is not general, e.g., the reaction of [Os(CO)-
(CS)(PPh3)3] with propyne proceeds via oxidative addition to
provide, inter alia, [OsH(CtCMe)(CO)(CS)(PPh3)2], and while
the alkynyl ligand of this complex does not itself undergo
migratory insertion, addition of HCl provides the thioacyl
derivative [Os(η2-SCCHdCHMe)Cl(CO)(PPh3)2] via the pre-
sumed intermediacy of vinylidene- and alkenyl-thiocarbonyl
complexes (Scheme 2).7f
a Legend: (i) PhCtCPh, -CO; (ii) HCtCMe; (iii) HCl; (iv) CO.
Herein, we report synthetic routes to a range of five-
coordinate electronically unsaturated alkenyl-thiocarbonyl com-
plexes of ruthenium(II), [Ru(CR1dCHR2)Cl(CS)(PPh3)2]. We
have previously reported briefly on the use of these complexes
in other studies9,10 and now provide full details of their
preparation and ligand addition-substitution chemistry. These
species are well-disposed for studying the migratory insertion
reactions of σ-alkenyl and thiocarbonyl ligands. The potential
of these complexes for the preparation of polymetallic ensembles
using 1,4-diethynylbenzene and a bridging dicarboxylate is also
demonstrated.
(2) (a) Bedford, R. B.; Hill, A. F.; Jones, C.; White, A. J. P.; Williams,
D. J.; Wilton-Ely, J. D. E. T. Organometallics 1998, 17, 4744. (b) Hill, A.
F.; Jones, C.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. J.
Chem. Soc., Dalton Trans. 1998, 1419. (c) Hill, A. F.; Jones, C.; White, A.
J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Chem. Commun. 1998, 367.
(d) Bedford, R. B.; Hill, A. F.; Jones, C.; White, A. J. P.; Williams, D. J.;
Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans. 1997, 1113. (e) Bedford,
R. B.; Hill, A. F.; Jones, C.; White, A. J. P.; Wilton-Ely, J. D. E. T. J.
Chem. Soc., Dalton Trans. 1997, 139. (f) Bedford, R. B.; Hill, A. F.; Jones,
C.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Chem. Commun.
1997, 179. (g) Bedford, R. B.; Hibbs, D. E.; Hill, A. F.; Hursthouse, M.
B.; Malik, K. M. A.; Jones, C. Chem. Commun. 1996, 1895. (h) Bedford,
R. B.; Hill, A. F.; Jones, C. Angew. Chem., Int. Ed. Engl. 1996, 35, 547.
(3) (a) Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1978, 159, 73.
(b) Roper, W. R.; Town, K. G. J. Chem. Soc., Chem. Commun. 1977, 781.
(c) Collins, T. J.; Roper, W. R. J. Chem. Soc., Chem. Commun. 1976, 1044.
(4) (a) Clark, G. R.; Collins, T. J.; Marsden, K.; Roper, W. R. J.
Organomet. Chem. 1978, 157, C23. (b) Clark, G. R.; Collins, T. J.; Marsden,
K.; Roper, W. R. J. Organomet. Chem. 1983, 259, 215.
Results and Discussion
The complex [RuHCl(CS)(PPh3)3] is available via thermal
decarboxylation of the bidentate formato complex [RuCl(κ2-
O2CH)(CS)(PPh3)2], which is in turn obtained from the reaction
of [RuCl2(OH2)(CS)(PPh3)2] with sodium formate.11 Heating a
suspension of [RuCl(O2CH)(CS)(PPh3)2] and diphenylacetylene
in ethanol under reflux leads to the formation of a bright orange
suspension of a complex formulated as [Ru(CPhdCHPh)Cl-
(CS)(PPh3)2] (1). The product shows virtually no change in the
thiocarbonyl infrared absorption observed at 1290 cm-1 (1292
cm-1 in the starting complex). However, the disappearance of
infrared bands attributed to the bidentate formato ligand (1545,
1358, and 810 cm-1) is conspicuous. Bands at 1597, 1587, and
1570 cm-1 appear in the spectrum of the product and are
(5) Rickard, C. E. F.; Roper, W. R.; Salter, D. M.; Wright, L. J.
Organometallics 1992, 11, 3931.
(6) (a) Irvine, G. J.; Lesley, M. J. G.; Marder, T. B.; Norman, N. C.;
Rice, C. R.; Robins, E. G.; Roper, W. R.; Whittell, G. R.; Wright, L. J.
Chem. ReV. 1998, 98, 2685. (b) Crossley, I. R.; Hill, A. F.; Willis, A. C.
Organometallics 2007, 26, 3891.
(7) (a) Clark, G. R.; Lu, G.-L.; Roper, W. R.; Wright, L. J. Organome-
tallics 2007, 26, 2167. (b) Elliott, G. P.; Roper, W. R. J. Organomet. Chem.
1983, 250, C5. (c) Elliott, G. P.; Roper, W. R.; Waters, J. M. J. Chem.
Soc., Chem. Commun. 1982, 811. (d) Clark, G. R.; Johns, P. M.; Roper,
W. R.; Wright, L. J. Organometallics 2006, 25, 1771. (e) Lu, G.-L.; Roper,
W. R.; Wright, L. J.; Clark, G. R. J. Organomet. Chem. 2005, 690, 972. (f)
Rickard, C. E. F.; Roper, W. R.; Woodgate, S. D.; Wright, L. J. J.
Organomet. Chem. 2001, 623, 109. (g) Hill, A. F.; Schultz, M.; Willis, A.
C. Organometallics 2005, 24, 2027.
(10) Wilton-Ely, J. D. E. T.; Honarkhah, S. J.; Wang, M.; Tocher, D.
A.; Slawin, A. M. Z. Dalton Trans. 2005, 1930.
(11) (a) Brothers, P. J.; Headford, C. E. L.; Roper, W. R. J. Organomet.
Chem. 1980, 195, C29. (b) Brothers, P. J.; Roper, W. R. J. Organomet.
Chem. 1983, 258, 73.
(8) The exception, to date, involves thioformyl complexes,3 all of which
appear to involve mondentate coordination.
(9) Cannadine, J.; Hector, A.; Hill, A. F. Organometallics 1992, 11, 2323.

6116 Organometallics, Vol. 26, No. 25, 2007
Cowley et al.
complex [Ru(CHdCH2)Cl(CS)(PPh3)2] (3) was similarly pre-
pared from the rapid reaction of a solution of [RuHCl(CS)-
(PPh3)3] with ethyne. While the resonance due to HR is obscured
by phosphine resonances, the geminal dCHâHâ′ group (see
Scheme 3 for notation) gives rise to two clear multiplets centered
at 4.68 and 5.08 ppm. The resonance to higher field (Hâ, JH H
R
â
) 14.2 Hz, JH H ′ ) 1.7 Hz) also shows broadening due to
â
â
coupling to phosphorus. Reaction between 1,4-diphenylb-
utadiyne and the hydride starting material provides the enynyl
complex [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4) by anal-
ogy with the previously reported carbonyl analogues [Ru{C(Ct
Figure 1. Molecular structure of 1 (phosphine phenyl groups and
phenyl hydrogen atoms omitted, 50% displacement ellipsoids).
Selected bond lengths (Å) and angles (deg): Ru-C ) 1.749(7),
Ru-Cl ) 2.4300(17), Ru-P(1) ) 2.4076(17), Ru-P(2) ) 2.4240-
(17), Ru-C(1) ) 2.045(6), C-S ) 1.574(7), C(1)-C(2) ) 1.351-
(8); P(1)-Ru-P(2) ) 171.45(6), Ru-C-S ) 176.7(5), C(2)-
C(1)-C(3) ) 124.1(6), Ru-C(1)-C(2) ) 132.5(5), Ru-C(1)-
C(3) ) 103.1(4).
t
n
CR)dCHR}Cl(CO)(PPh3)2] (R ) C6H5, C6H4Me, Bu, Bu,
CMe2OH, SiMe3).12 The molecular structure of this complex
was also confirmed by a crystallographic study (Figure 2).
The single alkenyl proton gives rise to a triplet resonance at
1
δ 5.50 (JHP ) 1.7 Hz) ppm in the H NMR spectrum. The
presence of an uncoordinated CtCPh triple bond is suggested
by a weak absorption at 2123 cm-1 in the solid-state infrared
spectrum (Nujol).
characteristic of the stilbenyl group in this and subsequent
derivatives. The 1H NMR data for the complex were of limited
use for characterization, and so the corresponding di-p-tolyl
derivative was also prepared by an analogous procedure. Infrared
data were similar and the 1H NMR data somewhat more
informative: the vinylic proton is observed to resonate at 5.58
ppm in the 1H NMR spectrum of the complex, and this
resonance shows poorly resolved weak coupling to two chemi-
cally equivalent phosphorus nuclei, suggesting a trans disposition
of the two phosphine ligands. In addition, two methyl resonances
and two (AB)2 patterns for the para-disubstituted C6H4 groups
indicate the chemical inequivalence of the two tolyl substituents.
The carbonyl analogue of the stilbenyl complex [Ru(CPhd
CHPh)Cl(CO)(PPh3)2] has been prepared previously1a from the
reaction of [RuHCl(CO)(PPh3)3] with diphenylacetylene and
structurally characterized. The formulation of [Ru(CPhdCHPh)-
Cl(CS)(PPh3)2] (1) was subsequently confirmed by a crystal-
lographic study, the results of which are summarized in Figure
1 and discussed below. Table 1 also summarizes relevant
dimensions for the complex [RuCl(CPhdCHPh)(CO)(PPh3)2]
for comparison, and these will be discussed below.
In contrast to the above results, the rapid reaction of [RuHCl-
(CS)(PPh3)3] with dimethyl acetylenedicarboxylate (DMAD)
rapidly provides the pale yellow complex [Ru{C(CO2Me)d
CHCO2Me}Cl(CS)(PPh3)2] (5). Five-coordinate σ-alkenyl com-
plexes of the form [Ru(CR1dCHR2)Cl(CA)(PPh3)2] (A ) O,
S) are typically brightly colored, and the pale color of this
derivative suggests that the σ-alkenyl ligand is in fact metal-
lacyclic in nature, with one of the methoxycarbonyl groups
acting as a sixth ligand to ruthenium, resulting in octahedral
coordination. Such a five-membered metallacycle is also formed
in the reaction of other ruthenium hydrido complexes with
DMAD.1,13,14 It is noteworthy that the formation of this type of
ligand ultimately requires the less common trans hydroruthen-
ation of the alkyne (cis-â geometry), concerted insertion
typically providing the trans-â stereochemistry. The possibility
of eventual chelation presumably provides the driving force for
the observed outcome, and a discussion of possible intramo-
lecular rearrangements of this type of ligand has been provided
by Stone.14 It should be noted that an equilibrium between
σ-alkenyl and σ-π-alkenyl coordination would also allow for
cis-trans isomerism of the vinyl ligand (Chart 2).
Addition of Ligands. A coordinatively saturated alkenyl
species was prepared by the reaction of [Ru(CHdCH2)Cl(CS)-
(PPh3)2] (3) with 2,1,3-benzoselenadiazole (BSD), which pro-
vides [Ru(CHdCH2)Cl(CS)(BSD)(PPh3)2] (6). As has been
previously noted,15 the BTD ligand has no reliably characteristic
spectroscopic features, due to the aromatic protons being
obscured by those of the phosphines in the 1H NMR spectrum.
Furthermore, the infrared absorptions for this ligand are typically
weak. Nevertheless, the ligand serves as a dramatic visible
chromophore, imparting intense colors to the derived complexes.
Thus, coordination of BSD to the deep red precursor provides
a bright yellow adduct. As with the precursor, clear resonances
The reaction sequence most likely proceeds via thermal
decarboxylation of the formato ligand to produce the coordi-
natively unsaturated (or solvated) hydrido complex “RuHCl-
(CS)(PPh3)2”, which then undergoes hydroruthenation of the
alkyne (Scheme 3). Thermolysis of [RuCl(κ2-O2CH)(CS)-
(PPh3)2] in the presence of triphenylphosphine is known to
produce the tris(phosphine) complex [RuHCl(CS)(PPh3)3].11 The
trans influence of the hydride ligand, combined with steric
pressures associated with the mer-Ru(PPh3)3 geometry in this
complex, labilizes the unique phosphine completely (31P NMR)
to yield the 16-electron hydrido species in solution. Accordingly,
[RuHCl(CS)(PPh3)3] reacts with diphenylacetylene when heated
in tetrahydrofuran under reflux (10 min) to provide the same
complex, [Ru(CPhdCHPh)Cl(CS)(PPh3)2] (1); however, the
formate decarboxylation route is practically more expedient. The
reaction of [RuHCl(CS)(PPh3)3] with alkynes is, however, more
generally applicable, allowing extension to terminal alkynes.
Thus, a solution of [RuHCl(CS)(PPh3)3] reacts with ethynyl-
benzene in dichloromethane at room temperature to provide the
trans-â-styryl derivative [Ru(CHdCHPh)Cl(CS)(PPh3)2] (2)
(Scheme 3). The stereochemistry of hydroruthenation follows
(12) (a) Hill, A. F.; Melling, R. P. J. Organomet. Chem. 1990, 396, C22.
(b) Hill, A. F.; Melling, R. P.; Thompsett, A. R. J. Organomet. Chem. 1991,
402, C8. (c) Wakatsuki, Y.; Yamazaki, H.; Kumgawa, N.; Satoh, T.; Satoh,
J. J. Am. Chem. Soc. 1991, 113, 9604. (d) Alcock, N. W.; Hill, A. R.;
Melling, R. P.; Thompsett, A. R. Organometallics 1993, 12, 641. (e) Hill,
A. F.; Harris, M. C. J.; Melling, R. P. Polyhedron 1992, 11, 781. (f) Xia,
H. P.; Yeung, R. C. Y.; Jia, G. Organometallics 1998, 17, 4762.
(13) Vessey, J. D.; Mawby, R. J. J. Chem. Soc., Dalton Trans. 1993,
51.
(14) Blackmore, T.; Bruce, M. I.; Stone, F. G. A. J. Chem. Soc., Dalton
Trans. 1974, 106.
(15) (a) Harris, M. C. J.; Hill, A. F. Organometallics 1991, 10, 3903.
(b) Harris, M. C. J.; Hill, A. F. J. Organomet. Chem. 1992, 438, 209. (c)
Herberhold, M.; Hill, A. F. J. Organomet. Chem. 1989, 377, 151. (d) Alcock,
N. W.; Hill, A. F.; Roe, M. S. J. Chem. Soc., Dalton Trans. 1990, 1737.
1
from the observation of a vinylic AB system in the H NMR
spectrum of the product (δH 8.65, 6.15 ppm; JAB ) 14.1 Hz).
The low-field resonance shows a further coupling of 2.9 Hz to
two chemically equivalent phosphorus nuclei, consistent with
this proton being R to the (Ph3P)2Ru unit. The parent ethenyl

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6117
Table 1. Selected Geometrical Data for Ruthenium(II) Alkenyl Complexesa
complex
Ru-CR
CR-Câ
Ru-CR-Câ
[Ru(CHdCHPh)(κ2-O2CMe)(CO)L2]1c
[Ru(CPhdCHPh)Cl(CO)L2]1a
2.030(15)
2.03(1)
1.294(14)
1.37(2)
1.35(1)
1.338(3)
1.33(2)
1.351(8)
1.32(2)
1.319(7)
1.33(1)
1.325(5)
1.32(1)
1.345(11)
1.330(3)
1.292(7)
1.337(3)
1.335(8)
1.41(7)
125.6(8)
130.7(9)
124.4(7)
134.89(14)
128.9(7)
132.5(5)
134(1)
128.7(5)
133.4(6)
125.2(4)
132.9(7)
131.1(6)
131.31(19)
130.3(5)
126.64(17)
122.7(5)
122(4)
[Ru(CHdCHPh)(κ2-O2CH)(CO)L2]1h
[Ru(CHdCHPh)(C13H9ClNO)(CO)L2]26
[Ru(CRdCHR)(O2COH)(CO)L2]1b
2.036(8)
2.0380(18)
2.044(9)
2.045(6)
2.05(1)
2.058(6)
2.063(7)
2.067(3)
2.067(8)
2.080(7)
2.083(2)
2.097(5)
2.102(2)
2.103(6)
2.12(5)
[Ru(CPhdCHPh)Cl(CS)L2] (1)
[Ru(CHdCHC3H7)Cl(CO)(Me2Hpz)L2]27
[Ru(CHdCHC6H4Me-4)(C4H5N2S)(CO)L2]10
[Ru(CHdCHtBu)Cl(CO)(HpzMe2)L2]1b
[Ru(CHdCHC6H4Me-4)(C5H4NO)(CO)L2]28
[Ru(CHdCHtBu){HNdC(Me)pzMe2}(CO)L2]+ 29
[Ru(CHdCH2){κ2-H2B(pz)2}(CO)L2]30
[Ru(CHdCH2)(C9H12NS)(CO)L2]28
[Ru(CHdCH2)(CO)([9]aneS3)L]+ 31
[Ru(CPhdCHPh)(C4H5N2S)(CS)L2]26
[Ru{C(OiPr)dCHPh}(η5-C5H5)(CO)L]32
[Ru(CRdCHR)(CO)(NCMe)2L2]+ 33
a L ) PPh3; R ) CO2Me. Distances are given in Å and angles in deg.
Scheme 3a
Chart 2. Alternative Rationales for Cis to Trans Isomerism
of â-Carboalkoxyvinyl Ligands (R ) CO2Me)
a L ) PPh3. Legend: (i) PhCtCPh; (ii) PPh3, heat;11b (iii) R1CtCR.2
(CO)(BSD)(PPh3)2],15d which readily hydroruthenates alkynes.
In some cases these hydroruthenation reactions proceed more
cleanly than those of the tris(phosphine) complex [RuHCl(CO)-
(PPh3)3], avoiding contamination by [Ru(alkenyl)Cl(CO)-
(PPh3)3]. Accordingly, the thiocarbonyl analogue [RuHCl(CS)-
(BSD)(PPh3)2] (7) was prepared by the reaction of [RuHCl(CS)-
(PPh3)3] with BSD in refluxing tetrahydrofuran. The geometry
at ruthenium is assumed to be the same as that established for
[RuHCl(CO)(BSD)(PPh3)2],15d i.e., that shown in Scheme 4,
involving trans phosphines and the coordination of the hydride
ligand cis to the BSD. The reaction of [RuHCl(CS)(BSD)-
(PPh3)2] (7) with ethyne ensues at room temperature to provide
[Ru(CHdCH2)Cl(CS)(BSD)(PPh3)2] (6) in high yield and is
probably accompanied by a change in geometry such that the
BSD ligand in the product resides trans to the σ-alkenyl ligand.
The osmium complex [Os(C6H4Me-4)Cl(CS)(PPh3)2]4 reacts
rapidly with carbon monoxide to provide the octahedral complex
[Os(C6H4Me-4)Cl(CS)(CO)(PPh3)2], with CS and σ-tolyl ligands
presumably coordinated adjacent to one another. This is
supported by the smooth thermal conversion of this compound
to the tautomeric species [Os(η2-SCC6H4Me-4)Cl(CO)(PPh3)2],
Figure 2. Molecular structure of 4 (phosphine phenyl groups and
phenyl hydrogen atoms omitted, 50% displacement ellipsoids).
Selected bond lengths (Å) and angles (deg): Ru(1)-C(17) ) 1.753-
(4), Ru(1)-Cl(1) ) 2.4313(10), Ru(1)-P(1) ) 2.4051(10), Ru-
(1)-P(2) ) 2.3904(10), Ru(1)-C(1) ) 2.027(4), C(17)-S(1) )
1.582(4), C(1)-C(10) ) 1.352(6), C(2)-C(3) ) 1.211(6); P(1)-
Ru(1)-P(2) ) 173.20(4), Ru(1)-C(17)-S(1) ) 179.2(3), C(10)-
C(1)-C(2) ) 127.2(4), Ru(1)-C(1)-C(10) ) 135.4(3), Ru(1)-
C(1)-C(2) ) 97.3(2), C(1)-C(2)-C(3) ) 170.0(4).
due to the CHâHâ′ group are apparent in the 1H NMR spectrum;
however, as a result of coordination of a strong donor ligand
trans to the alkenyl ligand, the resonance due to HR becomes
shifted to lower field of the phosphine resonances (8.18 ppm).
The related carbonyl complexes [Ru(alkenyl)Cl(CO)(BSD)-
(PPh3)2]15 may be prepared from the hydrido complex [RuHCl-

6118 Organometallics, Vol. 26, No. 25, 2007
Cowley et al.
Scheme 5. Alkenyl-Thiocarbonyl Couplinga
Scheme 4a
a L ) PPh3. Legend: (i) BSD; (ii) HCtCH.
which features a η2-thiatoluoyl ligand. A crystal structure
determination of the corresponding trifluoroacetato complex
[Os(η2-SCC6H4Me-4)(O2CCF3)(CO)(PPh3)2] confirmed the η2
formulation.4a Similar chemistry has been observed for the
osmium σ-alkenyl complex [Os(CPhdCHPh)Cl(CS)(PPh3)2].7b
In contrast, the carbonyl complexes [RuRX(CO)(PPh3)2] (R )
σ-aryl,16 σ-alkenyl;1 X ) Cl, Br, I) react with CO to provide
mixtures of either the dicarbonyl complex [RuRX(CO)2(PPh3)2]
or the tautomeric η2-acyl complex [Ru(η2-OCR)X(CO)(PPh3)2],
the position of the equilibrium depending on the nature of R,
X, and solvent.
a L ) PPh3. Legend: (i) CO.
consistent with the σ-alkenyl group now being remote from
ruthenium (Scheme 5).
Although a preliminary decolorization of the reaction mixture
prior to rapid darkening is sometimes briefly discernible, the
failure to more definitely observe or isolate an intermediate
octahedral thiocarbonyl complex in the reactions of [Ru(CR1d
CHR2)Cl(CS)(PPh3)2] with carbon monoxide is consistent with
the generally recognized acceleration in reaction rates on moving
from osmium to ruthenium. In the reaction of the bis-
(carbomethoxy) derivative [Ru{C(CO2Me)dCHCO2Me}Cl-
(CS)(PPh3)2] (5) with CO, however, no migratory insertion
reaction is observed under mild conditions. Instead, the stable
octahedral σ-alkenyl-thiocarbonyl complex [Ru{C(CO2Me)d
CHCO2Me}Cl(CS)(CO)(PPh3)2] (12) is isolated. The coordina-
tion of carbon monoxide requires that the metallacycle in the
precursor be opened to release a free coordination site, and the
rapidity of this reaction suggests that this opening is facile. The
retardation of the migratory insertion may be traced to two
plausible factors. The kinetic site of CO coordination may be
the site cis to the alkenyl ligand liberated by opening of the
chelate. If so, this may place the thiocarbonyl trans to the
σ-alkenyl ligand and thus not available for CS-alkenyl cou-
pling. Alternatively, coordination of CO trans to the thiocar-
bonyl ligand would result in the appropriate geometry and,
furthermore, the trans disposition of CS and CO ligands
would especially activate the thiocarbonyl to migratory insertion.
Thus, the reticence for migratory insertion is most likely
attributable to the increase in Ru-C bond strength that results
from inclusion of electron-withdrawing methoxycarbonyl sub-
stituents, considered to enhance metal-carbon multiple bonding
(Chart 2).
Clearly, addition of BSD to the alkenyl-thiocarbonyl com-
plexes above does not induce migratory insertion coupling of
these two ligands. The outcomes of reactions of 1-4 with carbon
monoxide are dependent on the nature of the alkenyl substitu-
ents: when the ruthenium σ-alkenyl complexes [Ru(CR1d
CHR2)Cl(CS)(PPh3)2] (R1 ) R2 ) Ph (1); R1 ) H, R2 ) Ph
(2); R1 ) R2 ) H (3); R1 ) CtCPh; R2 ) Ph (4)) were treated
with carbon monoxide (1 atm), a rapid darkening of the solution
to deep red occurred and migrated complexes formulated as
[Ru(η2-SCCR1dCHR2)Cl(CO)(PPh3)2] (R1 ) R2 ) Ph (8); R1
) H, R2 ) Ph (9); R1 ) R2 ) H (10); R1 ) CtCPh; R2 ) Ph
(11)) could be isolated in high yield. The infrared absorption
due to the thiocarbonyl ligand is no longer evident; however,
bands of medium intensity at 1332, 1288, 1263, 1193, 966, 929,
and 881 cm-1 (Nujol) are observed, which may be attributed
to the RuCS metallacycle (Scheme 5). A similar pattern of bands
is observed for the osmium4,17 and ruthenium18 thioaroyl
complexes. The thioacyl carbon gives rise to a triplet resonance
at 306.0 ppm (JCP ) 8.9 Hz) in the 13C{1H} NMR spectrum of
8, downfield from that assigned to the carbonyl ligand (δC 210.2,
1
t, JCP ) 15.2 Hz). The H NMR spectrum of [Ru(η2-SCCHd
CHPh)Cl(CO)(PPh3)2] (9) is informative: the AB pattern (δH
6.56, 6.35) due to the trans-â-styryl group shows a much
reduced difference in the chemical shifts of the two protons,
loss of resolvable phosphorus coupling to the low-field doublet,
and a modest increase in the value of JAB to 15.1 Hz, all
The complexes [Ru(CHdCH2)Cl(CS)(PPh3)2] (3) and [Ru-
{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4) both undergo migratory
insertion coupling of alkenyl and thiocarbonyl ligands upon
carbonylation. In the case of the enynyl species, no resolvable
phosphorus coupling with the alkenyl proton resonance is
observed. This is in contrast to that seen for the precursor, thus
confirming the remoteness of the alkenyl group. The formulation
of the complex [Ru{η2-SCC(CtCPh)dCHPh}Cl(CO)(PPh3)2]
(11) was subsequently confirmed by a crystallographic study,
the results of which are summarized in Figure 3 and discussed
below.
(16) (a) Roper, W. R.; Taylor, G. E.; Waters, J. M.; Wright, L. J. J.
Organomet. Chem. 1979, 182, C46. (b) Bohle, D. S.; Clark, G. R.; Rickard,
C. E. F.; Roper, W. R.; Wright, L. J. J. Organomet. Chem. 1988, 358, 411.
(c) Rickard, C. E. F.; Roper, W. R.; Taylor, G. E.; Waters, J. M.; Wright,
L. J. J. Organomet. Chem. 1990, 389, 375.
(17) Hill, A. F.; Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans.
1998, 3501.
(18) Bedford, R. B.; Hill, A. F.; White, A. J. P.; Williams, D. J. Angew.
Chem., Int. Ed. Engl. 1996, 35, 95.

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6119
Scheme 7a
Figure 3. Molecular structure of 11 (phosphine phenyl rings and
phenyl hydrogen atoms omitted, 50% displacement ellipsoids).
Selected bond lengths (Å) and angles (deg): Ru-C ) 1.952(7),
Ru-S ) 2.552(2), Ru-Cl ) 2.501(2), Ru-P(1) ) 2.407(2), Ru-
P(2) ) 2.400(2), Ru-C(17) ) 1.829(10), C-S ) 1.651(11),
C-C(1) ) 1.459(12), C(1)-C(2) ) 1.341(13), C(3)-C4) ) 1.156-
(12); C-Ru-S ) 40.3(3), P(1)-Ru-P(2) ) 172.05(8), Ru-C-S
) 89.8(4), Ru-S-C ) 49.9(3), C(1)-C(3)-C(4) ) 176.3(11).
a L ) PPh3. Legend: (i) Na[O2CH] or FcCO2H, NEt3 (Fc )
CpFeC5H4); (ii) Fe(η5-C5H4CO2H)2, NEt3.
Scheme 6a
The reactions of the complexes [Ru(alkenyl)Cl(CO)(PPh3)2]
with carboxylates give air-stable coordinatively saturated com-
plexes of the type [Ru(alkenyl)(κ2-O2CR)(CO)(PPh3)2] with no
significant side products.1c,f,h,21 Bis(carboxylates) therefore
presented an alternative approach to the preparation of binuclear
complexes. In order to test the reactivity of the thiocarbonyl-
alkenyl complexes with carboxylates, [Ru(CHdCH2)Cl(CS)-
(PPh3)2] (3) was treated with sodium formate, resulting in the
clean formation of [Ru(CHdCH2)(κ2-O2CH)(CS)(PPh3)2] (14)
through substitution of the chloride ligand and occupation of
the vacant site (Scheme 7). The presence of the formate ligand
was indicated by a phosphorus-coupled triplet resonance in the
1H NMR spectrum at 7.00 ppm (JHP ) 1.8 Hz). The HR
resonance of the ethenyl ligand was obscured by those of the
phosphine ligands, but its presence was manifest in coupling
to the Hâ and Hâ′ protons, signals for which appear at δH 4.84
(dt) and 5.01 (dt). In addition to the diagnostic νOCO band at
1547 cm-1, a characteristically strong infrared absorption was
observed for the thiocarbonyl ligand at 1274 cm-1 (Nujol),
indicating that the halide/formate metathesis does not induce
migratory insertion.
a L ) PPh3. Legend: (i) HCtCC6H4CøτFâ≡CH; (ii) CO.
In the chemistry of alkenyl complexes bearing carbonyl
ligands, 1,4-diethynylbenzene has been used to prepare dinuclear
complexes19 and recent studies have investigated the electro-
chemical properties of the triisopropylphosphine variants.20 The
conjugation of the p-phenylene unit also makes these species
attractive for studies of charge-transfer processes. It appeared
likely that the methodology described above would provide a
route to an unprecedented bis(thioacyl) complex linked by the
p-SCCHdCH(C6H4)CHdCHCS “spacer”. Reaction of 2 equiv
of [RuHCl(CS)(PPh3)3] with 1,4-diethynylbenzene led to a
purple solution, which 31P NMR spectroscopy revealed to be a
mixture of products (likely to include some tris(phosphine)
species). Treatment of this solution with carbon monoxide
resulted in a darkening of the color to deep red, and from this
solution a brown solid was obtained (Scheme 6) and formulated
as [(PPh3)2(CO)ClRu(η2-SCCHdCHC6H4CHdCHCS-η2)RuCl-
(CO)(PPh3)2]2 (13). Evidence for this included the presence of
a νCO band at 1918 cm-1 and, more importantly, the absence
of a thiocarbonyl absorption in the solid-state infrared spec-
trum. The only feature observed for the protons of the
An analogous yellow-orange product, [Ru{C(CtCPh)d
CHPh}(κ2-O2CFc)(CS)(PPh3)2] (15; Fc ) CpFeC5H4), was
formed in excellent yield from the reaction of enynyl complex
4 with ferrocenecarboxylic acid in the presence of NEt3.
Ferrocenemonocarboxylate complexes of ruthenium have previ-
ously been reported,22a including the alkenyl derivative [Ru-
(CHdCH2)(O2CFc)(CO)(PPh3)2].22b Characteristic resonances
1
were observed for the enynyl ligand in the H NMR spectrum
along with pseudotriplets at 3.88 and 4.03 ppm (JHH ) 1.65
Hz) for the monosubstituted cyclopentadienyl ring and a singlet
at 3.49 ppm for the C5H5 ligand. The formulation of the complex
was subsequently confirmed by elemental analysis and a
crystallographic study, the results of which are summarized in
Figure 4 and discussed below.
1
p-phenylene spacer in the H NMR spectrum was a singlet at
6.98 ppm (as expected on symmetry grounds) along with
resonances for the alkenyl protons at 6.43 and 6.53 ppm (JHH
) 15.5 Hz), similar to those observed for [Ru(η2-SCHdCHPh)-
Cl(CO)(PPh3)2] (9).
This result paved the way for the synthesis of a trimetallic
bridged alkenyl species using 1,1′-ferrocenedicarboxylic acid
(21) Loumrhari, H.; Ros, J.; Ya´n˜ez, R.; Torres, M. R. J. Organomet.
Chem. 1991, 408, 233.
(22) (a) Matas, L.; Moldes, I.; Soler, J.; Ros, J.; Alvarez-Larena, A.;
Piniella, J. F. Organometallics 1998, 17, 4551. (b) Wyman, I. W.; Burchell,
T. J.; Robertson, K. N.; Cameron, T. S.; Aquino, M. A. S. Organometallics
2004, 23, 5353.
(19) (a) Santos, A.; Lo´pez, J.; Montoya, J.; Noheda, P.; Romero, A.;
Echavarren, A. M. Organometallics 1994, 13, 3605. (b) Jia, G.; Wu, W.
F.; Yeung, R. C. Y.; Xia, H. P. J. Organomet. Chem. 1997, 539, 53.
(20) Maurer, J.; Sarkar, B.; Schwederski, B.; Kaim, W.; Winter, R. F.;
Za´lisˇ, S. Organometallics 2006, 25, 3701.

6120 Organometallics, Vol. 26, No. 25, 2007
Cowley et al.
Figure 4. Molecular structure of 15 (phosphine phenyl groups and
cyclopentadienyl and phenyl hydrogen atoms omitted, 50% dis-
placement ellipsoids). Selected bond lengths (Å) and angles (deg):
Ru-C ) 1.778(5), Ru-P(1) ) 2.3872(15), Ru-P(2) ) 2.4134-
(15), Ru-C(1) ) 2.069(5), Ru-O(18) ) 2.250(4), Ru-O(19) )
2.237(3), C-S ) 1.565(6), C(1)-C(2) ) 1.346(7), C(3)-C(4) )
1.182(7); P(1)-Ru-P(2) ) 176.66(5), O(18)-Ru-O(19) ) 58.16-
(13), Ru-C-S ) 174.4(4), Ru-C(1)-C(2) ) 129.6(4), C(1)-
C(3)-C(4) ) 172.4(6).
Figure 6. Superposition of the equatorial coordination planes of
Ru(CPhdCHPh)Cl(CA)(PPh3)2 (A ) O1a (red), S (blue)).
while it is not isomorphous with the carbonyl analogue, the
molecular geometries at ruthenium are superficially similar for
both complexes.
The gross coordination geometry at ruthenium may be
described as between trigonal bipyramidal (tbp) and square-
based pyramidal (sbp), with an angle of 171.45(6)° between
the ruthenium-phosphorus vectors and 121.7(2)° for C-Ru-
Cl. In the case of the corresponding carbonyl analogue, the
σ-vinyl ligand may be described as assuming the apical-sbp site.
For 1, this description is less apt, in that the alkenyl ligand makes
an angle close to 90° (93.3(3)°) with the thiocarbonyl ligand
and 145.0(2)° with the chloride. Thus, it would appear that it is
the thiocarbonyl ligand that is best described as occupying the
apical-sbp site, as illustrated in Figure 6, consistent with both
the superlative π-acidity and trans influence of CS ligands. The
plane of the alkenyl linkage is essentially normal to that
containing the ruthenium-phosphorus bonds (77.35°), consistent
with the ligand adopting a π-acid role which is maximized in
this orientation, in addition to minimizing nonbonding interac-
tions. The assertion of partial multiple bonding between Ru and
C1 of the alkenyl ligand is supported by a comparatively short
Ru-C1 separation of 2.045(6) Å, which falls toward the shorter
end of the range for σ-alkenyl ligands bound to divalent
ruthenium (Table 1). Furthermore, the vinylic separation of
1.351(8) Å is somewhat long for such ligands.
Given the comparatively small set of structurally characterized
pairs of carbonyl and thiocarbonyl complexes, it is worthwhile
to consider the bonding within the equatorial planes of both
molecules in more detail (Figure 6 and Table 1). First, the
ruthenium-chalcocarbonyl bond is clearly enhanced in the
thiocarbonyl complex, with a 2% decrease in the Ru-C bond
length relative to that of the analogous carbonyl ligand. On
comparison of the ruthenium-alkenyl separations for the two
complexes, there is a marginal lengthening of the bond in the
thiocarbonyl complex. The ruthenium center is less π-basic in
this complex, due to the enhanced π-acidity of the thiocarbonyl
Figure 5. Molecular structure of the complex 16 (phosphine phenyl
groups and cyclopentadienyl and phenyl hydrogen atoms omitted,
50% displacement ellipsoids). A crystallographic C2 axis passes
through Fe. Selected bond lengths (Å) and angles (deg): Ru-C )
1.783(8), Ru-P(2) ) 2.395(2), Ru-P(1) ) 2.383(2), Ru-C(1) )
2.053(9), Ru-O(18) ) 2.253(5), Ru-O(19) ) 2.250(5), C-S )
1.560(8), C(1)-C(2) ) 1.358(11), C(3)-C(4) ) 1.208(13); P(1)-
Ru-P(2) ) 175.23(8), O(18)-Ru-O(19) ) 58.81(18), Ru-C-S
) 175.5(5), Ru-C(1)-C(2) ) 130.0(7), C(1)-C(3)-C(4) ) 168.7-
(10).
as the bifunctional linker. Treatment of 2 equiv of 4 with 1
equiv of the dicarboxylic acid in the presence of excess Et3N
led to the formation of the trinuclear complex Fe[η5-C5H4CO2-
Ru{C(CtCPh)dCHPh}(CS)(PPh3)2]2 (16). Spectroscopic data
similar to those for 15 were obtained, and the molecular structure
of this species was confirmed by a crystallographic study. These
results are summarized in Figure 5 and discussed below.
Given the abundance of carboxylic acids available, and the
many known mononuclear complexes,1c,f,h,15 it is perhaps
surprising that bridging carboxylate units have not been used
to link ruthenium centers in the manner described above. The
closest examples are those reported very recently, in which 2
equiv of [Ru(aryl)Cl(CO)(PPh3)2] (aryl ) C6H2OH-2-CHNC6H4R;
R ) Me, Cl) reacts with disodium terephthalate to give [Ru-
(aryl)(CO)(PPh3)2]2(µ-O2CC6H4CO2).23 However, despite an
increasing number of polymetallic compexes bridged by the
ferrocenedicarboxylate ligand having appeared in recent times,24
it is also surprising that none appear to be of the simple dinuclear
monobridged form {LnMO2CC5H4}2Fe but instead involve
polymeric structures or bridged metal-metal multiple bonded
bimetallic units.
(24) (a) Kim, Y. S.; Kim, J.; Kim, D.; Chae, H. K. Chem. Lett. 2007,
36, 150. (b) Yeng, X.; Li, G.; Hou, H.; Han, H.; Fan, Y.; Zhu, Y.; Du, C.
J. Organomet. Chem. 2003, 679, 153. (c) Dong, G.; Li, Y.-T.; Duan, C.-
Y.; Hong, M.; Meng, Q.-J. Inorg. Chem. 2003, 42, 2519. (d) Naksakov, V.
A.; Slovohotova, I. V.; Golovin, A. V.; Babailov, S. P. Russ. Chem. Bull.
2001, 50, 2451. (e) Bera, J. K.; Clerac, R.; Fanwick, P. E.; Walton, R. A.
Dalton Trans. 2002, 2168. (f) Cotton, F. A.; Donahue, J. P.; Lin, C.; Murillo,
C. A. Inorg. Chem. 2001, 40, 1234. (g) Lee, S.-M.; Cheung, K.-K.; Wong,
W.-T. J. Organomet. Chem. 1996, 506, 77. (h) Cayton, R. H.; Chisholm,
M. H.; Huffman, J. C.; Lobkovsky, E. B. J. Am. Chem. Soc. 1991, 113,
8709. (i) Xiangru, M.; Hongwei, H.; Gang, L.; Baoxian, Y.; Tiezhu, G.;
Yaoting, F.; Yu, Z.; Sakiyama, H. J. Organomet. Chem. 2004, 689, 1218.
(j) Xiangru, M.; Gang, L.; Hongwei, H.; Huayun, H.; Yaoting, F.; Yu, Z.;
Chenxia, D. J. Organomet. Chem. 2003, 679, 153. (k) Dong, G.; Hong,
M.; Duan, C.-Y.; Feng, L.; Qing-Jin, M. Dalton Trans. 2002, 2593.
Structural Discussion. Despite coordinative unsaturation, the
complex [Ru(CPhdCHPh)Cl(CS)(PPh3)2] (1) is monomeric, and
(23) Pan, S.; Panda, B. K. J. Indian Chem. Soc. 2005, 82, 16.

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6121
Table 2. Geometrical Data for Ruthenium and Osmium Thioacyl Complexesa
complex
M-C
M-S
C-S
S-Ru-C
[Os(η2-SCR)(O2CCF3)(CO)L2]3a
[Ru{η2-SCC(CtCPh)dCHPh}Cl(CO)L2] (11)
[Ru(η2-SCSiMe2OEt)Cl(CO)L2]5
[Ru(η2-SCSMe)(CO)2L2]+ 34
1.91(2)
2.513(6)
2.552(2)
2.545(2)
2.459(4)
2.548(2)
2.455(2)
2.596
1.72(2)
43.0(5)
40.3(3)
40.0(2)
42.2(4)
41.4(3)
42.5(2)
39.4
1.952(7)
1.978(8)
2.043(13)
1.959(8)
2.047(5)
1.975
1.651(11)
1.637(8)
1.667(13)
1.687(9)
1.674(5)
1.646
[Ru(η2-SCNMe2)Cl(CO)L2]35
[Ru(η2-SCNMe2)(CO)2L2]+ 35
18
[Ru(η2-SCPh)Cl(CS)L2
[Ru(SCSMe)(CO)(CNR)L2]+ 36
1.99(2)
2.63(2)
1.79(3)
43.7(7)
a L ) PPh3; R ) C6H4Me-4. Distances are given in Å and angles in deg.
Table 3. Selected Bond Data for Divalent Ruthenium σ1-Enynyl Complexesa
complex
Ru-CR
CR-Câ
CR-Câ′
Câ′-Cγ
Ru-CR-Câ
Fe[C5H4CO2RuR(CS)L2]2 (16)
[RuR(O2CFc)(CS)L2] (15)
[RuRCl(CS)L2] (4)
2.053(9)
2.069(5)
2.027(4)
2.076(8)
2.090(12)
2.102(2)
2.109(4)
2.111(3)
2.111(4)
2.155(3)
2.094(7)
1.358(11)
1.346(7)
1.352(6)
1.354(16)
1.374(19)
1.361(3)
1.336(5)
1.362(3)
1.340(5)
1.372(4)
1.349(10)
1.404(12)
1.429(8)
1.415(5)
1.437(12)
1.40(2)
1.420(3)
1.422(5)
1.428(4)
1.421(6)
1.397(4)
1.422(11)
1.208(13)
1.182(7)
1.211(6)
1.208(3)
1.22(2)
1.205(3)
1.207(6)
1.199(3)
1.205(6)
1.223(4)
1.182(10)
130.0(7)
129.6(4)
135.4(3)
128.5(6)
122(1)
126.48(17)
135.4(3)
124.74(19)
126.1(3)
125.8(2)
129.3(6)
[RuR(O2CCF3)(CO)L2]37
[RuR{HB(pz)3}(CO)L]38
[RuR(C3H4NS2)(CO)L2]39
[RuR′Cl(CO)L2]12c
[RuR(C9H12NS)(CO)L2]26
[RuR(C4H4N3S)(CO)L2]28
40
[RuR′′Cl(CO)2L2
[RuR(dppm)(Ind)41
t
a R ) CR(Câ′tCγPh)dCâHPh, R′ ) CR(Câ′tCγ Bu)dCâHtBu; R′′ ) CR(Câ′tCγX)dCâHX (X ) CtW(CO)2HB(pzMe2)3); Ind ) η5-C9H7; L ) PPh3.
Distances are given in Å and angles in deg.
ligand, and this might be expected to be reflected in a
compromise of any retrodonation from ruthenium to the alkenyl
ligand.
1) canonical forms. The failure of the complex to coordinate
further ligands by opening the metallacycle might, however,
argue for a more substantial contribution from form C.
Data for related group 8 “metallathiirenes”3a,c,28 are collected
in Table 2, and these suggest that geometrical changes within
the metallacycle are more responsive to variations in the thioacyl
substituent than to the metal or complex charge. These infer-
ences should be made with caution, given the limited amount
of structural data so far available.
A comparison of the stereochemistry of the equatorial planes
of the two complexes in addition to related arrangements for
the complexes [Ru(C6H4Me-n)Cl(CO)(PPh3)2] (n ) 2, 4)11c
indicates that the energies involved in moving between the ideal
trigonal-bipyramidal and square-based-pyramidal geometries
(the latter calculated to be favored for d6 configurations25) must
be small and may well be of a magnitude comparable to
intramolecular packing forces. Furthermore, there are clear
indications that the coordinative unsaturation in these complexes
may be at least partially stabilized by weak interactions with
ortho hydrogen atoms of the phosphine ligands.
A similar structure midway between tbp and sbp is found
for [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4). A difference
between the structures is the slightly shorter Ru(1)-C(1)
distance of 2.027(4) Å in 4 (cf. 1). The geometries of the alkyne
carbons C(2) and C(3) are appreciably nonlinear, with the Ct
C triple bond being bent slightly toward the metal atom. The
Ru‚‚‚C(2) and Ru‚‚‚C(3) distances are 2.615(4) and 3.383(4)
Å, with angles at C2 and C3 being 170.0(4) and 175.7(4)°,
respectively.
The thioacyl complex [Ru{η2-SCC(CtCPh)dCHPh}Cl(CO)-
(PPh3)2] (11) is monomeric in the crystal, with no significant
intermolecular contacts. Considering the thioacyl to occupy one
coordination site, the gross geometry may be described as a
mildly distorted trigonal bipyramid with trans-axial phosphine
ligands (P1-Ru-P2 ) 172.05(8)°). The orientations of the
equatorial atoms of the first coordination sphere are such that
π-donors (S and Cl) are pseudo-trans to π-acidic groups
(carbonyl C7 and acyl carbon C), thereby maximizing synergy
in π-interactions. Within the metallathiirene unit there is clear
multiple bonding between C and Ru (1.952(7) Å) and C and S
(1.651(11) Å). These data are consistent with contributions from
both the thioacyl (B, Chart 1) and the metallathiirene (C, Chart
The compound [Ru{C(CtCPh)dCHPh}(κ2-O2CFc)(CS)-
(PPh3)2] (15) displays close to octahedral geometry about the
ruthenium center with cis interligand angles in the range 83.66-
(10)-106.25(19)°. The Ru-C1 and C1-C2 bond distances are
compared with those of other enynyl complexes, in which the
alkenyl ligand is bound directly to ruthenium in a monodentate
manner, in Table 3. The enynyl group (excluding the phenyl
substituents) in compound 15 lies in the same plane as the
ferrocenecarboxylate chelate, the thiocarbonyl ligand, and the
metal center. The alkenyl group substituents are arranged in an
E configuration as a corollary of the synthetic route, rather than
a manifestation of steric or electronic factors. The O18-Ru-
O19 angle of 58.16(13)° is essentially comparable (8 esd) to
that of 59.24(13)° reported for the related carboxylate complex
[Ru(CRdCHR)(O2CCHdCMe2)(CO)(PPh3)2] (R ) CO2Me).1d
It is also worth noting that while the Ru-O bond distance trans
to the carbonyl ligand in this carboxylate complex is similar to
that found in 15, the length of the Ru-O17 bond (trans to
alkenyl, 2.237(4) Å) is somewhat greater than the corresponding
Ru-O bond in the literature complex (2.161(3) Å, 23 esd). This
might be explained by the greater π-acidity of the carbomethoxy
groups (cf. Ph and CtCPh) being transmitted through the vinyl
ligand, thereby enhancing any π-dative component of the
carboxylate binding. The geometry at the alkynyl substituent is
(26) Wilton-Ely, J. D. E. T.; Wang, M.; Honarkhah, S.; Tocher, D. A.
Inorg. Chim. Acta 2005, 358, 3218.
(27) Torres, M. R.; Santos, A.; Perales, A.; Ros, J. J. Organomet. Chem.
1988, 353, 221.
(25) (a) Pearson, R. G. J. Am. Chem. Soc. 1969, 91, 4947. (b) Hoffman,
P. R.; Caulton, K. G. J. Am. Chem. Soc. 1975, 97, 4221.
(28) Wilton-Ely, J. D. E. T.; Pogorzelec, P. J.; Honarkhah, S.; Reid, D.
H.; Tocher, D. A. Organometallics 2005, 24, 2862.

6122 Organometallics, Vol. 26, No. 25, 2007
Cowley et al.
close to linear, with a C1-C3-C4 angle of 172.4(6)°. The P1-
Ru-P2 angle of 176.66(5)° is also close to linear, indicating
that there is little steric interaction between the ferrocenyl group
and the phenyl substituents on the phosphines. The Ru-C bond
length for the thiocarbonyl ligand of 1.778(5) Å might be
expected to be considerably shorter than that for the Ru-CO
bond (1.808(4) Å) in [Ru(CRdCHR)(O2CCHdCMe2)(CO)-
(PPh3)2] (R ) CO2Me); however, these are essentially compa-
rable (within 7 esd).
functionalization of the 16-electron thiocarbonyl alkenyl com-
plexes [RuRCl(CS)(PPh3)3] (R ) CHdCH2, CCtCPhdCHPh),
either through the substituent of the alkenyl group or the vacant
site at the metal center. Crystallographic studies show that the
trimetallic complex Fe[κ2-C5H4CO2Ru{C(CtCPh)dCHPh}-
(CS)(PPh3)2]2 hinges on the iron atom of the ferrocenylcar-
boxylate ligand while the rigidity of the spacer ligand in the
species [(Ph3P)2(OC)ClRu(η2-SCCHdCHC6H4CHdCHCS-η2)-
RuCl(CO)(PPh3)2]2 ensures a linear rigid-rod arrangement.
The two ruthenium centers in the trinuclear compound Fe-
[C5H4CO2Ru{C(CtCPh)dCHPh}(CS)(PPh3)2]2 (16) are crys-
tallographically identical (being related by a rotation axis) and
display an octahedral geometry with cis interligand angles
between 86.08(15) and 108.2(3)°, the shortest being due to the
carboxylate chelate bite. The geometrical data for the complex
are similar to those for 15. There is a slight distortion from
linearity along the Ru-Fe-Ru′ axis, causing the ferrocenyl Cp
rings to show an eclipsed configuration. This effect is most likely
due to crystal-packing constraints rather than any steric interac-
tion of the enynyl groups which are placed on the same side of
the Ru-Fe-Ru′ axis.
Experimental Section
General Comments. All experiments were carried out under
aerobic conditions unless otherwise stated. The majority of the
complexes appear indefinitely stable toward the atmosphere in
solution or in the solid state, with the exception of the intermediate
R,ω-divinyl intermediate in the synthesis of 13, which slowly
deteriorates in solution. Solvents were used as received from
commercial sources. The complexes [RuCl(κ2-O2CH)(CS)(PPh3)2]
and [RuHCl(CS)(PPh3)3] have been described elsewhere.11 Infrared
and FAB-MS data were obtained using Mattson Research Series
FT-IR and Autospec Q instruments, respectively. Characteristic
phosphine-associated infrared data are not reported. NMR spec-
troscopy was performed in CDCl3 at 25 °C using a JEOL JNM
EX270 spectrometer. Virtual triplet 13C NMR resonances are written
as tv, and these indicate a trans disposition of phosphine ligands
(with “apparent” couplings quoted). All couplings are in hertz.
Elemental analysis data were obtained from the Imperial College
Microanalytical service or SACS at London Metropolitan Univer-
sity. Light petroleum refers to the petroleum ether fraction of boiling
point range 40-60 °C. The procedures given provide materials of
sufficient purity for synthetic and spectroscopic purposes. Samples
were recrystallized from a mixture of dichloromethane and ethanol
for elemental analysis. Solvates were confirmed by integration of
Concluding Remarks
While the hydroruthenation chemistry of [RuHCl(CS)(PPh3)2-
(L)] (L ) PPh3, BSD) appears to parallel that observed for
[RuHCl(CO)(PPh3)2(L)], the reactions of the compounds pro-
duced with CO are dominated by the greater propensity of the
thiocarbonyl ligand to participate in migratory insertion reac-
tions. The metal-carbon bond strength of carbon monosulfide
exceeds that of carbon monoxide due to more efficient σ-dona-
tion and π-retrodonation. However, it is the latter feature (low-
lying π* orbitals of CS) that also make the M-C bond more
reactive, in the present case with respect to migratory insertion.
These factors might also be expected to be reflected in the
relative M-C interactions of η2 acyl vs thioacyl ligands, wherein
one d(π)-p(π) retrodative interaction is retained. However, the
interaction between sulfur and the soft ruthenium or osmium
centers and the accompanying reduction in C-S p(π)-p(π)
multiple bonding are presumably also important factors.42 Two
diruthenium alkenyl complexes have also been prepared using
different approaches. Both made use of the potential for further
1
the H NMR spectrum.
Preparation of [Ru(CPhdCHPh)Cl(CS)(PPh3)2] (1). (a) A
solution of [RuHCl(CS)(PPh3)3] (200 mg, 0.207 mmol) in tetrahy-
drofuran (10 mL) was treated with diphenylacetylene (70 mg, 0.393
mmol) and heated under reflux for 10 min. The solution was cooled,
diluted with ethanol (30 mL), and concentrated under reduced
pressure to provide orange crystals which were isolated by filtration,
washed with ethanol (2 × 10 mL) and light petroleum (10 mL),
and dried under vacuum. Yield: 140 mg (77%).
(b) A suspension of [RuCl(κ2-O2CH)(CS)(PPh3)2] (200 mg, 0.267
mmol) and diphenylacetylene (70 mg, 0.393 mmol) in ethanol (20
mL) was heated under reflux for 1 h. The orange suspension was
left to cool for 1 h and the orange microcrystalline product isolated
by filtration, washed with ethanol (2 × 10 mL) and light petroleum
(10 mL), and dried under vacuum. Yield: 190 mg (81%). Further
material (ca. 5%) could be obtained by removal of solvent from
the filtrate and crystallization of the residue from a mixture of
chloroform and ethanol. IR (Nujol, cm-1): 1596, 1586, 1570, 1564,
(29) Lo´pez, J.; Santos, A.; Romero, A.; Echavarren, A. M. J. Organomet.
Chem. 1993, 443, 221.
(30) Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T.
Organometallics 1998, 17, 4249.
(31) Cannadine, J. C.; Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-
Ely, J. D. E. T. Organometallics 1996, 15, 5409.
(32) Bruce, M. I.; Duffy, D. N.; Humphrey, M. G.; Swincer, A. G. J.
Organomet. Chem. 1985, 282, 385.
(33) Lo´pez, J.; Romero, A.; Santos, A.; Vegas, A.; Echavarren, A. M.;
Noheda, P. J. Organomet. Chem. 1989, 373, 249.
(34) Clark, G. R.; Collins, T. J.; James, S. M.; Roper, W. R. J.
Organomet. Chem. 1977, 125, C23.
(35) Hill, A. F.; Tocher, D. A.; Whiet, A. J. P.; Williams, D. J.; Wilton-
Ely, J. D. E. T. Organometallics 2005, 24, 5342.
(36) Boniface, S. M.; Clark, G. R. J. Organomet. Chem. 1980, 184, 125.
(37) Dobson, A.; Moore, D. S.; Robinson, S. D.; Hursthouse, M. B.;
New, L. Polyhedron 1985, 4, 1119.
(38) Alcock, N. W.; Hill, A. F.; Melling, R. P. Organometallics 1991,
10, 3898.
(39) Wilton-Ely, J. D. E. T.; Wang, M.; Benoit, D. M.; Tocher, D. A.
Eur. J. Inorg. Chem. 2006, 3068.
(40) Dewhurst, R. D.; Hill, A. F.; Smith, M. K. Organometallics 2005,
24, 6295.
1
1290 νCS, 1153, 970, 921, 875, 842, 829, 791. H NMR: 5.64 (s
(br), 1 H, RuCdCH), 6.47, (d × 2, 2 H, H2,6(CC6H5), JHH ) 7.6),
6.90 (m, 2 H, H3,5(CC6H5)), 7.20 (t, 1 H, H4(CC6H5), JHH ) 7.4),
7.26-7.56 (m, 35 H, PC6H5 + CC6H5) ppm. 13C{1H} NMR: 301.2
(t, CS, JCP ) 17.0), 166.1 (t, RuCPh, JCP ) 9.0), 138.8 (s (br),
C1(CC6H5), JPC not resolved), 136.3 (tv, o-/m-PC6H5, JPC ) 5.4),
133.9 (tv, o-/m-PC6H5, JPC ) 5.4), 137.2-127.3 (m, remaining
PC6H6, CC6H5 and CHPh) ppm. 31P{1H} NMR: 31.3 ppm. FAB-
MS: m/z (% abundance) 884 (15) [M]+, 849 (26) [M - Cl]+, 705
(8) [M - alkenyl]+, 670 (32) [M - Cl - alkenyl]+, 622 (7) [M -
PPh3]+, 586 (60) [M - Cl - PPh3]+, 407 (24) [Ru(CS)(PPh3)]+,
363 (24) [RuPPh3]+. Anal. Found: C, 61.7; H, 4.1. Calcd for
C51H41ClP2RuS‚CHCl3: C, 62.2; H, 4.2.
(41) Bassetti, M.; Marini, S.; Diaz, J.; Gamasa, M. P.; Gimeno, J.;
Rodriguez-Alvarez, Y.; Garcia-Granda, S. Organometallics 2002; 21, 4815.
(42) Headford, C. E. L.; Roper, W. R. In Reactions of Coordinated
Ligands; Braterman, P. S., Ed.; Plenum Press: New York, 1985; Vol. 1,
pp 513-552.
The complex [Ru{C(C6H4Me-4)dCHC6H4Me-4}Cl(CS)(PPh3)2]
was also prepared in comparable yield for NMR purposes by a

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6123
completely analogous procedure, with diphenylacetylene being
replaced by di-p-tolylacetylene: a solution of [RuHCl(CS)(PPh3)3]
(200 mg, 0.207 mmol) in tetrahydrofuran (20 mL) was treated with
di-p-tolylacetylene (85 mg, 0.412 mmol) and the resulting mixture
heated under reflux for 2.5 h and then cooled to room temperature.
Ethanol (30 mL) was added and the mixture concentrated under
reduced pressure to ca. 10 mL. The crude brown precipitate was
isolated by filtration and recrystallized from a mixture of dichlo-
romethane and ethanol. Yield: 145 mg (77%). IR (Nujol): 1278
PPh3]+, 611 (100) [M - PPh3]+, 407 (60) [Ru(CS)PPh3]+, 363
(14) [RuPPh3]+ Anal. Found: C, 67.6; H, 4.8. Calcd for C53H41-
ClP2RuS‚0.5CH2Cl2: C, 67.6; H, 4.5.
Preparation of [Ru{C(CO2Me)dCHCO2Me}Cl(CS)(PPh3)2]
(5). A solution of [RuHCl(CS)(PPh3)3] (200 mg, 0.207 mmol) in
dichloromethane (10 mL) was treated with dimethyl acetylenedi-
carboxylate (0.15 mL, 1.217 mmol) and stirred for 10 min. The
yellow solution was diluted with ethanol (20 mL) and concentrated
under reduced pressure to provide yellow crystals of the product.
These were isolated by filtration, washed with ethanol (2 × 10
mL) and light petroleum (10 mL), and dried under vacuum. Yield:
150 mg (85%). The product can be recrystallized from chloroform-
ethanol mixtures. IR (Nujol): 1722, 1693 νCdO, 1600, 1573, 1336,
ν
CS, 1187, 1158, 807 δ(C6H4) cm-1. 1H NMR: 2.20 (s, 3 H, Me),
2.21 (s, 3 H, Me), 5.57 (s (br), 1 H, dCH), 6.29, 6.48 (AB, 4 H,
C6H4, JAB ) 7.9), 6.63, 6.77 (AB, 4 H, C6H4, JAB ) 7.9), 7.09-
7.70 (m, 30 H, PC6H5). 31P{1H} NMR: 31.2 ppm.
1
1284 νCS, 1223, 1006, 916, 1256, 889, 853 cm-1. H NMR: 2.89
Preparation of [Ru(CHdCHPh)Cl(CS)(PPh3)2] (2). A solution
of [RuHCl(CS)(PPh3)3] (200 mg, 0.207 mmol) in dichloromethane
(10 mL) was treated with phenylacetylene (0.15 mL, 1.371 mmol)
and stirred for 10 min. The solution was diluted with ethanol (40
mL) and stirred for a further 15 min. Red crystals of the product
were isolated by filtration, washed with ethanol (2 × 10 mL) and
light petroleum (10 mL), and dried under vacuum. Yield: 120 mg
(s, 3 H, CH3), 3.54 (s, 3 H, CH3), 4.98 (t, 1 H, dCH, JHP ) 1.5
Hz), 7.25-7.80 (m, 30 H, C6H5) ppm. 31P{1H} NMR: 32.6 ppm.
FAB-MS: not diagnostic. Anal. Found: C, 57.4; H, 3.7. Calcd for
C43H37ClO4P2RuS‚0.5CHCl3: C, 57.5; H, 4.2.
Preparation of [Ru(CHdCH2)Cl(CS)(BSD)(PPh3)2] (6). [Ru-
(CHdCH2)Cl(CS)(PPh3)2] (3; 180 mg, 0.246 mmol) was dissolved
in dichloromethane (5 mL) and 2,1,3-benzoselenadiazole (60 mg,
0.328 mmol) added. Ethanol (10 mL) was then added and the
mixture stirred for 30 min, during which time a yellow solid
precipitated from solution. This was filtered off, washed with
ethanol (10 mL) and hexane (10 mL), and dried under vacuum.
(72%). IR (Nujol): 1593, 1585, 1571, 1565, 1552, 1285, 1270 νCS
,
1148, 973, 963, 950, 930, 921, 800 cm-1. H NMR (C6D6): 6.15
(d, 1 H, dCâH, JHH ) 14.1), 6.83-7.13, 7.85-7.95 (m × 2, 30 H
+ 5 H, C6H5), 8.65 (dt, 1 H, RuCH, JHH ) 14.1, JHP ) 2.9) ppm.
31P{1H} NMR: 33.5 ppm. FAB-MS: m/z (% abundance) 808 (1)
[M]+, 773 (11) [M - Cl]+, 705 (2) [M - alkenyl]+, 671 (1) [M -
Cl - alkenyl]+, 626 (1) [Ru(PPh3)2]+, 443 (4) [M - alkenyl -
PPh3]+, 397 (4) [RuClPPh3]+, 365 (10) [RuPPh3]+. Anal. Found:
C, 65.7; H, 4.8. Calcd for C45H37ClP2RuS‚0.25CH2Cl2: C, 65.5;
H, 4.6.
1
Yield: 180 mg (80%). IR (Nujol): 1585, 1560, 1513, 1313, 1271
1
ν
CS, 1236, 1136, 1116, 917, 889, 843, 814 cm-1. H NMR: 5.06
(d, 1 H, Hâ, JH H ) 16.8), 5.59 (d, 1 H, Hâ′, JH H ′ ) 8.6), 7.11-
R
â
R â
7.57 (m, 34 H, C6H5 + C6H4N2Se), 8.18 (m, 1 H, HR) ppm.
31P{1H} NMR: 26.1 ppm. FAB-MS: m/z (% abundance) 863 (4)
[M - C4H4]+, 836 (2) [M - SCCHCH2]+. 697 (5) [M - BSD -
Cl]+, 669 (4) [M - alkenyl - Cl - BSD]+, 433 (3) [HM - BSD
- PPh3 - Cl]+, 407 (7) [Ru(CS)(PPh3)]+, 263 (25) [HPPh3]+. Anal.
Found: C, 58.9; H, 4.1; N, 3.0. Calcd for C45H37ClN2P2RuSSe:
C, 59.1; H, 4.1; N, 3.1.
Preparation of [Ru(CHdCH2)Cl(CS)(PPh3)2] (3). [RuHCl-
(CS)(PPh3)3] (400 mg, 0.413 mmol) was dissolved in dichlo-
romethane (40 mL) and acetylene bubbled through the solution for
30 s. After it was stirred under an atmosphere of acetylene for 40
min, the solution was diluted with ethanol (25 mL). Slow
concentration provided orange crystals of the product, which were
isolated by filtration, washed with ethanol (2 × 10 mL) and light
petroleum (10 mL), and dried under vacuum. Yield: 250 mg (83%).
IR (Nujol): 1586, 1567, 1548, 1269 νCS, 1230, 1208, 1186, 969,
Preparation of [RuHCl(CS)(BSD)(PPh3)2] (7). A suspension
of [RuHCl(CS)(PPh3)3] (310 mg, 0.320 mmol) in tetrahydrofuran
(30 mL) was treated with 2,1,3-benzoselenadiazole (120 mg, 0.656
mmol). The mixture was heated under reflux for 1 h and then cooled
and diluted with ethanol (30 mL). The solvent volume was reduced
slowly, resulting in the formation of olive green crystals. These
were filtered off, washed with ethanol (20 mL) and hexane (20
mL), and dried under vacuum. Yield: 270 mg (95%). IR (Nujol):
1
868, 852 cm-1. H NMR: 4.68 (dd, 1 H, Hâ, JH H ) 14.2, JH H ′
â
R
â â
) 1.7), 5.08 (m, 1 H, Hâ′), 7.30-7.67 (m, 31 H, HR and C6H5)
ppm. 13C{1H} NMR: 296.5 (t, CS, JCP ) 15.2), 155.1 (t, RuCH,
JCP ) 9.8), 134.6 (tv, o-/m-PC6H5, JCP ) 5.4), 131.1 (tv, i-PC6H5,
JCP ) 23.2), 130.2 (s, p-PC6H5), 128.2 (tv, o-/m-PC6H5, JCP ) 5.3),
119.0 (s, RuCdC) ppm. 31P{1H} NMR: 32.2 ppm. FAB-MS: m/z
(% abundance) 697 (10) [M - Cl]+, 669 (2) [M - alkenyl]+, 443
(5) [M - PPh3 - alkenyl]+, 407 (4) [M - Cl - alkenyl]+. Anal.
Found: C, 63.9; H, 4.7. Calcd for C39H33ClP2RuS: C, 64.0; H,
4.5.
1
2052, 2027 νRuH, 1716, 1585, 1570, 1266 νCS cm-1. H NMR:
-10.46 (t, 1 H, RuH, JHP ) 19.3), 6.87-7.68 (m, 34 H, C6H5 +
C6H4) ppm. 31P{1H} NMR: 43.6 ppm. FAB-MS: m/z (% abun-
dance) 836 (2) [M - C4H4]+, 705 (2) [M - H - BSD]+, 669 (2)
[M - H - Cl - BSD]+. Anal. Found: C, 58.0; H, 4.0; N, 2.9.
Calcd for C43H35ClN2P2RuSSe: C, 58.1; H, 4.0; N, 3.2.
Preparation of the Complexes [Ru(η2-SCCR1dCHR2)Cl(CO)-
(PPh3)2] (R1 ) R2 ) H, Ph; R1 ) H, R2 ) Ph; R1 ) CtCPh,
R2 ) Ph) and [Ru{C(CO2Me)dCHCO2Me}Cl(CO)(CS)(PPh3)2].
A stream of carbon monoxide was passed through a solution of
the respective complex [Ru(CR1dCHR2)Cl(CS)(PPh3)2] (1-4) or
[Ru{C(CO2Me)dCHCO2Me}Cl(CS)(PPh3)2] (5) (0.20 mmol) in
dichloromethane (10 mL) for 10 s and then the mixture stirred for
5 min. The solution was diluted with ethanol (40 mL) and stirred
for a further 10 min. The resulting crystals of the product were
isolated by filtration, washed with ethanol (2 × 10 mL) and light
petroleum (10 mL), and dried under vacuum. Yield: spectroscopi-
cally quantitative (31P NMR).
Preparation of [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4).
[RuHCl(CS)(PPh3)3] (300 mg, 0.310 mmol) and 1,4-diphenylbuta-
1,3-diyne (130 mg, 0.64 mmol) were suspended in tetrahydrofuran
(20 mL) and heated under reflux for 10 min. The solution was
cooled and diluted with ethanol (30 mL). Bright orange crystals of
the product were obtained on concentration under reduced pressure
and isolated by filtration. These were washed with ethanol (2 ×
10 mL) and light petroleum (10 mL) and dried under vacuum.
Yield: 230 mg (82%). IR (Nujol): 1719, 1586, 1570, 1279 νCS
,
1
955, 914, 845 cm-1. H NMR: 5.50 (t, 1 H, dCâH, JHP ) 1.7),
7.09, 7.07, 7.06 (m × 3, CC6H5), 7.15-7.75 (m, 30 H, PC6H5)
ppm. 13C{1H} NMR: 300.5 (t, CS, JCP ) 16.1), 142.8 (t, RuC, JCP
) 8.0), 138.4 (RuCdC), 135.0 (tv, o-/m-PC6H5, JCP ) 5.4), 130.6
(tv, i-PC6H5, JCP ) 22.3), 130.0 (p-PC6H5), 128.3 (C6H5), 127.8
(tv, o-/m-PC6H5, JCP unresolved), 126.2, 125.5 (s × 2, C6H5), 123.8,
120.1 (s × 2, CtC) ppm. 31P{1H} NMR: 33.1 ppm. FAB-MS:
m/z (% abundance) 908 (66) [M]+, 873 (97) [M - Cl]+, 705 (23)
[M - alkenyl]+, 669 (10) [M - Cl - alkenyl]+, 646 (10) [M -
[Ru(η2-SCCPhdCHPh)Cl(CO)(PPh3)2] (8). IR (CH2Cl2): 1913
ν
CO, 1602, 1584, 1572, 1563 cm-1. IR (Nujol): 1915 νCO, 1582,
1562, 1312, 1256, 1205, 1155, 1144, 951, 939, 915, 889, 845, 818
1
cm-1. H NMR: 5.99 (d, 2 H, C2,6(C6H5), JHH ) 7.3), 6.75 (d, 2
H, H2,6(C6H5), JHH ) 7.6), 7.14 (m, H3,5(C6H5)), 7.38 (s, 1 H,
CHPh), 7.28-7.77 (m, 30 H, PC6H5) ppm. 13C{1H} NMR: 306.0

6124 Organometallics, Vol. 26, No. 25, 2007
Cowley et al.
(t, CS, JCP ) 8.9), 210.2 (t, CO, JCP ) 15.2), 154.6, 152.3, 144.2
(CC6H5 and dCHPh), 140.1-126.0 ppm (m, PC6H5 + CC6H5,
individual assignments equivocal). 31P{1H} NMR: 30.2 ppm. FAB-
MS: m/z (% abundance) 912 (3) [M]+, 884 (83) [M - CO]+, 877
(100) [M - Cl]+, 849 (2) [M - Cl - CO]+, 689 (20) [M -
SCCPhdCHPh]+, 622 (22) [M - CO - PPh3]+, 615 (18) [M -
Cl - PPh3]+, 586 (79) [M - Cl - CO - PPh3]+, 363 (24)
[RuPPh3]+, 324 (27) [M - Cl - CO - 2PPh3]+. Anal. Found: C,
64.1; H, 3.4. Calcd for C52H41ClOP2RuS‚CH2Cl2: C, 63.8; H, 4.4.
mg (57%). IR (CH2Cl2): 1918 νCO, 1589 cm-1. IR (Nujol): 1906
ν
CO, 1719, 1584, 1547, 1324, 1238, 961, 936, 888, 846, 815 cm-1
.
1H NMR: 6.43, 6.53 (AB, 4 H, CHdCH, JAB ) 15.5), 6.98 (s, 4
H, C6H4), 7.28-7.83 (m, 30 H, PC6H5) ppm. 13C{1H} NMR: not
sufficiently soluble. 31P{1H} NMR: 29.5 ppm. FAB-MS: m/z (%
abundance) 1566 (47) [M - CO]+, 1301 (100) [M - CO - PPh3]+,
1267 (31) [M - Cl - PPh3]+. Anal. Found: C, 63.3; H, 4.2. Calcd
for C86H68Cl2O2P4Ru2S2‚0.5CH2Cl2: C, 63.5; H, 4.3.
Preparation of [Ru(CHdCH2)(κ2-O2CH)(CS)(PPh3)2] (14).
[Ru(CHdCH2)Cl(CS)(PPh3)2] (3; 90 mg, 0.123 mmol) was dis-
solved in dichloromethane (15 mL), and ethanol (10 mL) was added.
Na[O2CH] (20 mg, 0.294 mmol) was added as a water (1 mL)-
ethanol (5 mL) solution. This prompted an instant color change of
solution to yellow. After the mixture was stirred for 15 min, all
solvent was removed, the crude product was dissolved in dichlo-
romethane (10 mL), and this solution was filtered through diato-
maceous earth to remove NaCl. Ethanol (10 mL) was added, and
pale yellow crystals of the product precipitated by rotary evapora-
tion. These were filtered, washed with ethanol (10 mL) and petrol-
eum ether (10 mL), and dried. Yield: 70 mg (77%). IR (CH2Cl2):
1605, 1548 νOCO cm-1. IR (Nujol): 1962, 1914, 1816, 1718, 1628,
1615, 1587, 1571, 1547 νOCO, 1334, 1312, 1274 νCS, 1238, 868,
800 cm-1. 1H NMR: 4.84 (dt, 1 H, Hâ, JH H ) 16.2, JH H ) 1.7),
[Ru(η2-SCCHdCHPh)Cl(CO)(PPh3)2] (9). IR (CH2Cl2): 1919
ν
CO, 1711, 1604, 1594, 1571 cm-1. IR (Nujol): 1911 νCO, 1716,
1616, 1592, 1571, 1332, 1293, 1264, 1194, 966, 927, 881, 790 cm-1
1H NMR: 6.33 (d, 1 H, Hâ, JH H ) 14.8), 6.55 (d, 1 H, HR, JH H
.
R
â
R â
) 14.8), 7.03 (d, 2 H, C2,6(C6H5), JHH ) 7.3), 7.36 (t, 2 H,
C3,5(C6H5), JHH ) 7.6), 7.18-7.85 (m, 31 H, PC6H5 and C4(CC6H5))
ppm. 31P{1H} NMR: 29.2 ppm. FAB-MS: m/z (abundance) 836
(4) [M]+, 808 (41) [M - CO]+, 801 (57) [M - Cl]+, 689 (3) [M
- SCCHdCHPh]+, 546 (15) [M - CO - PPh3]+, 511 (11) [M -
Cl - CO - PPh3]+, 363 (8) [RuPPh3]+. Anal. Found: C, 64.6; H,
4.0. Calcd for C46H37ClOP2RuS‚0.25CH2Cl2: C, 64.8; H, 4.4. [Ru-
(η2-SCCHdCH2)Cl(CO)(PPh3)2] (10). IR (CH2Cl2): 1921 νCO
cm-1. IR (Nujol): 1930, 1913 νCO, 1717, 1616, 1588, 1572, 1306,
1
1289, 1237, 1192, 965, 892, 832 cm-1. H NMR: 4.71 (dd, 1 H,
R
â
â P
Hâ′, JH H ’ ) 9.9, JH H ) 1.0), 5.23 (dd, 1 H, Hâ, JH H ) 16.8,
5.01 (dt, 1 H, Hâ′, JH H ′ ) 9.2, JH ′H ) 2.1), 7.00 (t, 1 H, O2CH,
R
R
â
R â
JH H )â 1.0), 6.03 (ddd, 1 H, HR, JH H ) 9.7, JH H ) 16.7),
R
â
â
P
JHP ) 1.8), 7.35-7.58 (m, 1 H + 30 H, HR + C6H5) ppm. 31P{1H}
NMR: 35.4 ppm. FAB-MS: m/z (% abundance) 697 (6) [M -
O2CH]+, 670 (1) [M - alkenyl - O2CH]+. Anal. Found: C, 64.8;
H, 4.9. Calcd for C40H34O2P2RuS: C, 64.8; H, 4.6.
′
′
â
â
R
â
R â
7.35, 7.78 (m × 2, 30 H, C6H5) ppm. 31P{1H} NMR: 29.1 ppm.
FAB-MS: m/z (% abundance) 760 (3) [M]+, 732 (46) [M - CO]+,
725 (52) [M - Cl]+, 689 (58) [M - SCCHdCH2]+, 654 (2) [M -
Cl - SCCHdCH2]+, 625 (3) [M - Cl - CO - SCCHdCH2]+,
470 (6) [M - CO - PPh3]+, 435 (7) [M - Cl - CO - PPh3]+.
Anal. Found: C, 58.5; H, 4.3. Calcd for C40H33ClOP2RuS‚
CH2Cl2: C, 58.3; H, 4.2.
Preparation of [Ru{C(CtCPh)dCHPh}(κ2-O2CFc)(CS)-
(PPh3)2] (15). [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4; 150 mg,
0.165 mmol) was dissolved in dichloromethane (10 mL) and
ferrocenecarboxylic acid (40 mg, 0.174 mmol) added, followed by
3 drops of triethylamine (excess). The solution darkened over 30
min of stirring. After 1 h, ethanol (10 mL) was added and the
solvent volume reduced on the rotary evaporator. The precipitated
orange-yellow solid was isolated by filtration, washed with ethanol
(5 mL) and hexane (10 mL), and dried. Yield: 160 mg (88%). IR
(CH2Cl2): 2158 νC≡C, 1504 νOCO, 1280 νCS cm-1. IR (Nujol): 2154
[Ru{η2-SCC(CtCPh)dCHPh}Cl(CO)(PPh3)2] (11). IR
(CH2Cl2): 1916 cm-1. IR (Nujol): 2193 νC≡C, 1909 νCO, 1595,
1579, 1555, 1324, 1258, 1193, 1180, 928, 920, 870, 843, 819 cm-1
.
1H NMR: 6.80 (s, 1 H, CdCH), 7.20-7.90 (m, 40 H, C6H5) ppm.
13C{1H} NMR: 304.8 (t, CS, JCP not resolved), 209.4 (t, CO, JCP
not resolved), 154.5 (CCtC), 138.0-125.0 (C6H5, individual
assignments equivocal), 123.2, 95.4 (CtC) ppm. 31P{1H} NMR:
29.4 ppm. FAB-MS: m/z (% abundance) 936 (2) [M]+, 908 (53)
[M - CO]+, 901 (100) [M - Cl]+, 689 (6) [RuCl(CO)(PPh3)2]+,
646 (10) [M - CO - PPh3]+, 625 (10) [Ru(PPh3)2]+, 611 (82) [M
- Cl - CO - PPh3]+, 533 (10) [M - Cl - CO - Ph - PPh3]+,
363 (18) [RuPPh3]+, 263 (72) [HPPh3]+. Anal. Found: C, 65.6;
H, 4.8. Calcd for C54H41ClOP2RuS‚0.75CH2Cl2: C, 65.8; H, 4.3.
ν
C≡C, 1594, 1573, 1544, 1500 νOCO, 1270 νCS, 973, 914, 835, 811
cm-1. 1H NMR: 3.49 (s, C5H5), 3.88 (pseudo-t, 2 H, C5H4, JHH
)
1.7), 4.03 (pseudo-t, C5H4, 2 H, JHH ) 1.7), 5.85 (t, 1 H, dCH,
JHP ) 1.7), 7.08-7.14 (m, C6H5), 7.18-7.70 (m, 30 H, PC6H5 +
C6H5) ppm. 31P{1H} NMR: 33.7 ppm. FAB-MS: m/z (% abun-
dance) 873 (4) [M - O2CFc]+, 669 (2) [M - alkenyl - O2CFc]+,
407 (14) [M - alkenyl - O2CFc - PPh3]+. Anal. Found: C, 64.6;
H, 4.4. Calcd for C62H50FeO2P2RuS‚CH2Cl2: C, 65.1; H, 4.5.
Preparation of Fe[µ-η5:κ2-C5H4CO2Ru{C(CtCPh)dCHPh}-
(CS)(PPh3)2]2 (16). [Ru{C(CtCPh)dCHPh}Cl(CS)(PPh3)2] (4;
130 mg, 0.143 mmol) was dissolved in dichloromethane (10 mL)
and 1,1′-ferrocenedicarboxylic acid (20 mg, 0.073 mmol) added,
followed by 3 drops of triethylamine (excess). The solution was
stirred for 20 h and ethanol (10 mL) added. The solvent volume
was reduced on the rotary evaporator. The precipitated yellow solid
was isolated by filtration, washed with ethanol (5 mL) and
petroleum ether (10 mL), and dried. Yield: 150 mg (52%). IR
(CH2Cl2): 2156 νC≡C, 1496 νOCO, 1280 νCS cm-1. IR (Nujol): 2156
[Ru{C(CO2Me)dCHCO2Me}Cl(CO)(CS)(PPh3)2] (12). IR
(CH2Cl2): 2029 νCO, 1706 νCdO, 1604 νCdO cm-1. IR (Nujol): 2009
ν
CO, 1703 νCdO, 1693 νCdO, 1583, 1574, 1319 νCS, 1213, 1187,
1161, 890, 868, 825 cm-1. H NMR: 3.31 (s, 3 H, CH3), 3.49 (s,
3 H, CH3), 5.28 (t, 1 H, dCHR, JHP ) 2.1), 7.26-7.79 (m, 30 H,
C6H5) ppm. 31P{1H} NMR: 27.7 ppm. FAB-MS: m/z (% abun-
dance) 877 (2) [M]+, 845 (20) [M - Cl]+, 813 (38) [M - Cl -
CO]+, 705 (15) [M - CO - CRdCHR]+, 689 (7) [RuCl(CO)-
(PPh3)2]+, 670 (7) [Ru(CS)(PPh3)2]+, 586 (7) [M - CO - PPh3]+,
551 (15) [M - Cl - CO - PPh3]+, 407 (22) [Ru(CS)PPh3]+, 363
(4) [RuPPh3]+. Anal. Found: C, 56.6; H, 3.7. Calcd for C44H37-
ClO5P2RuS‚CH2Cl2: C, 56.2; H, 4.1.
1
ν
C≡C, 1592, 1492 νOCO, 1392, 1357, 1270 νCS, 973, 912, 835, 809
1
cm-1. H NMR: 3.60 (pseudo-t, C5H4, 8 H, JHH ) 1.8), 5.85 (s
(br), 2 H, dCH), 7.46-7.71 (m, 60 H + 20 H, PC6H5 + C6H5)
Preparation of [(PPh3)2(CO)ClRu(η2-SCCHdCHC6H4CHd
CHCS-η2)RuCl(CO)(PPh3)2]2 (13). [RuHCl(CS)(PPh3)3] (300 mg,
0.310 mmol) and 1,4-diethynylbenzene (20 mg, 0.159 mmol) were
dissolved in dichloromethane (20 mL), prompting a color change
to purple after 30 min of stirring. Ethanol (15 mL) was added and
carbon monoxide passed through the solution for 20 s. The flask
was stoppered and stirred and the addition repeated. After 30 min
of stirring, a brown solid was filtered, and on washing with diethyl
ether (30 mL), this became dark brick red and was further washed
with ethanol (10 mL) and hexane (10 mL) and dried. Yield: 280
ppm. 13C{1H} NMR (1:4 CDCl3-CH2Cl2): 302.5 (t, CS, JCP
)
16.1), 180.8 (s, O2C), 142.4, 139.6 (s × 2, CtCPh), 135.0 (tv, o-/
m-PC6H5, JCP ) 5.4), 131.7 (s, C6H5), 130.2 (tv, i-PC6H5, JCP
)
21.4), 129.8 (s, p-PC6H5), 128.1 (s, C6H5), 127.6 (tv, o-/m-PC6H5,
JCP unresolved), 126.9, 126.2, 124.7 (s × 3, C6H5), 76.0 (s,
i-PC5H4), 70.0 (s, o-/m-C5H4), 68.7 (s, o-/m-C5H4) ppm. 31P{1H}
NMR: 33.0 ppm. FAB-MS: m/z (% abundance) 2012 (28) [M -
6]+, 1757 (30) [M - PPh3]+, 1553 (14) [M - alkenyl - PPh3]+,

FiVe-Coordinate Complexes of Ruthenium(II)
Organometallics, Vol. 26, No. 25, 2007 6125
Table 4. Crystal Data and Data Collection and Refinement Parameters for Compounds 1, 4, 11, 15, and 16a
1
4
11
15
16
chem formula
solvent
C51H41ClP2RuS
CHCl3
C53H41ClP2RuS
CH2Cl2
C54H41ClOP2RuS
EtOH
C64H50FeO2P2RuS
CHCl3
C118H90FeO4P4Ru2S2
2Et2O
formula wt
temp (K)
cryst color, habit
cryst size (mm)
cryst syst
space group
a (Å)
1003.73
293(2)
993.38
150
orange blocks
0.10 × 0.14 × 0.18
triclinic
P1h (No. 2)
12.1475(2)
12.2581(2)
18.0528(3)
75.0004(7)
78.8495(7)
63.7609(10)
2319.31(7)
2
982.46
293(2)
1221.33
293(2)
2166.13
293(2)
orange prismatic blocks
0.40 × 0.37 × 0.13
orthorhombic
P212121 (No. 19)
12.9182(18)
17.933(2)
deep red blocks
0.22 × 0.14 × 0.12
monoclinic
P21 (No. 4)
11.8799(8)
17.3422(9)
12.0943(11)
orange rhomboids
0.40 × 0.38 × 0.22
orthorhombic
Pbca (No. 61)
22.7759(19)
18.791(4)
orange blocks
0.23 × 0.20 × 0.10
monoclinic
I2/a (No. 15)
24.287(3)
b (Å)
c (Å)
13.5739(12)
34.451(10)
20.0578(17)
26.845(3)
R (deg)
â (deg)
102.544(7)
95.559(10)
γ (deg)
V (Å3)
4646.6
4
2432.2(3)
2
11489(3)
8
11 304(4)
4b
Z
Dc (g/mL)
radiation used
µ(Mo KR) (mm-1
2θmax/deg
1.435
Mo KR
0.717
50
4548
3369
1.442
Mo KR
0.662
1.341
Cu KR
4.452
120
3750
3531
1.412
Mo KR
0.791
50
10 104
5848
1.273
Cu KR
4.447
120
8214
5098
)
no. of unique rflns measd
no. of obsd rflns |Fo| > 4σ(|Fo|)
no. of variables
10 505
6508
550
462
0.040, 0.082
488
0.047, 0.125
629
0.061, 0.132
547
0.075, 0.186
R1, wR2c
0.044, 0.051
a Details in common: graphite-monochromated radiation, refinement based on F2. b The complex has crystallographic C2 symmetry. c R1 ) ∑||Fo| -
2
2
2
2
|Fc||/∑|Fo|; wR2 ) {∑[w(Fo - Fc )2]/∑[w(Fo )2]}1/2; w-1 ) σ2(Fo ) + (aP)2 + bP.
1492 (55) [M - 2PPh3]+, 1231 (100) [M - 3PPh3]+, 1146 (64)
[M - Ru - CS - alkenyl - 2PPh3]+. Anal. Found: C, 68.0; H,
4.4. Calcd for C118H90FeO4P4Ru2S2‚CH2Cl2: C, 68.0; H, 4.4.
Crystallography. Single crystals of complexes 1, 4, 11, 15, and
16 were obtained by slow diffusion of ethanol into solutions of the
complexes in dichloromethane, and these were mounted on glass
fibers for data collection. Table 4 provides a summary of the
crystallographic data for compounds 1, 4, 11, 15, and 16. Data were
collected using Siemens P4 (1 and 15) and Enraf-Nonius Kap-
paCCD (4) and P4/RA (11 and 16) diffractometers, and the
structures were refined on the basis of F2 using the SHELXTL and
SHELX-97 program systems.43 The absolute structures of 1 and
11 were determined by a combination of R factor tests (for 1 R1+
Hydrogen atoms were positioned geometrically after each cycle of
refinement. A three-term Chebychev polynomial weighting scheme
was applied. The crystallographic data for the structures of 1, 4,
11, 15, and 16 have been deposited with the Cambridge Crystal-
lographic Data Centre as supplementary publication numbers CCDC
637444-637448, respectively. Copies of the data can be obtained
free of charge on application to The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, U.K. (fax, int. code +44 (1223) 336-
033; e-mail for inquiry, fileserv@ccdc.cam.ac.uk).
Acknowledgment. We are grateful to the EPSRC (U.K.)
for funding and diffractometry equipment. A.F.H. wishes to
thank the Department of Chemistry, University of Auckland,
for the provision of research facilities, Johnson Matthey
Chemicals Ltd for a generous loan of ruthenium salts, and the
Australian Research Council (Grant No. DP0556236) for
financial support. J.D.E.T.W.-E. wishes to acknowledge Merton
College, Oxford, U.K., for the provision of a fellowship.
) 0.0404 and R1- ) 0.0426; for 11 R1+ ) 0.0468 and R1-
)
0.0506) and by use of the Flack parameter (for 1 x+ ) +0.00(5)
and x- ) +1.14(5); for 11 x+ ) +0.15(3) and x- ) +0.85(3)).
Intensity data for 4 were processed using the DENZO-SMN
package,44 and the structure was solved using the direct-methods
program SIR92,45 which located all non-hydrogen atoms. Subse-
quent full-matrix least-squares refinement was carried out using
the CRYSTALS program suite.46 Coordinates and anisotropic
thermal parameters of all non-hydrogen atoms were refined.
Supporting Information Available: CIF files giving full details
of the crystal structure determinations of 1, 4, 11, 15, and 16.
This material is available free of charge via the Internet at
http://pubs.acs.org.
(43) SHELXTL PC, version 5.1; Bruker AXS, Madison, WI, 1997.
Sheldrick, G. SHELX-97; Institut Anorganische Chemie, Tammannstr. 4,
D-37077 Go¨ttingen, Germany, 1998.
(44) Otwinowski, Z.; Minor, W. Processing of X-ray Diffraction Data
Collected in Oscillation Mode. Methods Enzymol. 1997, 276.
(45) Altomare, A.; Cascarano, G.; Giacovazzo, G.; Guagliardi, A.; Burla,
M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.
OM700518M
(46) Betteridge, P. W.; Cooper, J. R.; Cooper, R. I.; Prout, K.; Watkin,
D. J. CRYSTALS, Issue 12. J. Appl. Crystallogr. 2003, 36, 1487.