Multimetallic arrays: Symmetrical and unsymmetrical bi-, tri-, and tetrametallic organometallic complexes of ruthenium(II) and osmium(II)

Article abstract of DOI:10.1021/om800686f

The cationic complex [Ru(C(C=CPh)=CHPhXS₂CNC4H ₈NH₂)(CO)(PPh₃)₂]⁺ was prepared from the reaction of [Ru(C(C=CPh)=CHPh)Cl(CO)(BTD)(PPh ₃)₂] (BID = 2,1,3-benzothiadiazol

Full text of DOI:10.1021/om800686f

Organometallics 2009, 28, 197–208
197
Multimetallic Arrays: Symmetrical and Unsymmetrical Bi-, Tri-,
and Tetrametallic Organometallic Complexes of Ruthenium(II) and
Osmium(II)
Mairi J. Macgregor,† Graeme Hogarth,‡ Amber L. Thompson,† and
James D. E. T. Wilton-Ely*,†
Chemistry Research Laboratory, UniVersity of Oxford, Mansfield Road, Oxford OX1 3TA, U.K., and
Department of Chemistry, UniVersity College London, 20 Gordon Street, London WC1H 0AJ, U.K.
ReceiVed July 20, 2008
The cationic complex [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ was prepared from the
reaction of [Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2] (BTD ) 2,1,3-benzothiadiazole) with the
zwitterionic dithiocarbamate H2NC4H8NCS2 and characterized structurally. In situ generation of the
metalladithiocarbamate [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NCS2)(CO)(PPh3)2] followed by treatment with
[Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2] yielded the symmetrical bimetallic complex
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}2(S2CNC4H8NCS2)]. The same product was also accessible by
reaction of KS2CNC4H8NCS2K with [Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2]. This direct method
also yielded the symmetrical bimetallic complexes [{Ru(CHdCHR)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (R
) But, CPh2OH, C6H4Me-4, CO2Me, CH2OSiMe2But) and a tetrametallic species when R ) C5H4FeC5H5.
The osmium analogues [{Os(CR1dCHR2)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (R1 ) Ct CPh, R2 ) Ph; R1
) H, R2 ) C6H4Me-4) were also prepared by this method. The stepwise deprotonation and functionalization
of [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ with NEt3 and CS2 was utilized in the generation
of the unsymmetrical complexes [{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru(CHdCHR)-
(CO)(PPh3)2}] (R ) But, CPh2OH, C6H4Me-4, CO2Me, CH2OSiMe2But, C5H4FeC5H5) and the hetero-
bimetallic variant [{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Os(CHdCHC6H4Me-4)(CO)(P-
Ph3)2}]. The mixed carbonyl-thiocarbonyl complex [{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CN-
C4H8NCS2){Ru(C(Ct CPh)dCHPh)(CS)(PPh3)2}] was also prepared by the same stepwise procedure.
These are the first reported examples of alkenyl species bridged by a dithiocarbamate ligand. The similarly
unprecedented linked bis(alkynyl)diruthenium complex [{Ru(Ct CBut)(CO)(PPh3)2}2(S2CNC4H8NCS2)]
was prepared by heating [{Ru(CHdCHC6H4Me-4)(CO)(PPh3)2}2(S2CNC4H8NCS2)] with excess HCt CBut.
The first molecular complex bearing all three group
8 metals, [{Ru(C(Ct CPh)dCHPh)-
(CO)(PPh3)2}(S2CNC4H8NCS2){Os(CHdCHFc)(CO)(PPh3)2}], was achieved through the reaction of
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ with [Os(CHdCHFc)Cl(CO)(BTD)(PPh3)2] -
(Fc ) C5H4FeC5H5, BTD ) 2,1,3-benzothiadiazole). Further trimetallic species [{Ru(C(Ct
CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2M] (M ) Ni, Pd, Pt, Zn) were prepared by the reaction of
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ with Ni(OAc)2, PdCl2(NCMe)2, PtCl2(NCPh)2,
and Zn(OAc)2 in the presence of NEt3 and CS2.
of a piperazine dithiocarbamate that exists as a zwitterion.4 This
species can be used to coordinate to a first metal center, while
retaining the potential to bond to a second on deprotonation
and functionalization with CS2 at the other end. A general
strategy for the synthesis of homo- and heterobimetallic
Introduction
Many transition-metal dithiocarbamate complexes are
known,1 and a number of these have found use in applications
as diverse as materials science, medicine, and agriculture. Their
extensive metal-centered electrochemistry2 and ability to sta-
bilize a wide range of oxidation states have proved to be key
factors in many applications. While polyfunctional variants of
many ligands have been used to create multimetallic systems,
this approach to dithiocarbamates has rarely been exploited.
Recent work to harness their versatility in the area of
supramolecular design has illustrated their utility in this regard.3
Our recent contributions in this area have centered on the use
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* To whom correspondence should be addressed. E-mail: james.wilton-
ely@chem.ox.ac.uk.
† University of Oxford.
‡ University College London.
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Chem. 2005, 4027–4030. (b) Wilton-Ely, J. D. E. T.; Solanki, D.; Knight,
E. R.; Holt, K. B.; Thompson, A. L.; Hogarth, G. Inorg. Chem.,in press.
10.1021/om800686f CCC: $40.75
2009 American Chemical Society
Publication on Web 12/02/2008

198 Organometallics, Vol. 28, No. 1, 2009
Scheme 1. General Scheme for the Generation of Bimetallic Complexes
Macgregor et al.
Scheme 2. Examples of Bimetallic Organotransition-Metal Compounds
complexes using a piperazine dithiocarbamate ligand is shown
in Scheme 1.
C(OR)CH2, (CH)2, (CH)4, (CH)6; B),7 or the linker is a diamine
(C), diisocyanide,7a or a bidentate dicarboxylate (D) unit.8 Sulfur
ligands are rarely used to link organometallic centers. An
unusual example is that reported by Shaver,9 in which a
diruthenium complex (E) is isolated from the reaction of 2 equiv
of [CpRu(PPh3)2SH] with p-phenylenediisothiocyanate while
reaction of [RuHCl(CS)(PPh3)3] with 1,4-diethynylbenzene
followed by treatment of carbon monoxide yields a bridging
thioacyl (F).8 Linked diosmium alkenyl complexes are extremely
rare, with only two known examples derived from the double
hydroosmiation of 1,3,5-triethynylbenzene.10
A particularly intriguing aspect is the accessibility of het-
erobimetallic systems using this route. However, to date the
metal units linked by such ligands5 have been simple coordina-
tion compounds, largely neglecting the bridging of organotransi-
tion-metal centers. Few bimetallic ruthenium complexes with
alkenyl ligands are known, and almost all are symmetrical in
nature.6 Some relevant examples of linked organometallics are
shown in Scheme 2. Either the alkenyl ligand is utilized to bridge
the metal centers (A, X ) C6H4, C6H4C6H4, CH2C(OR)-
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Bi-, Tri-, and Tetrametallic Complexes of Ru(II) and Os(II)
Organometallics, Vol. 28, No. 1, 2009 199
None of these methods is widely applicable to the preparation
of unsymmetrical heterobimetallic organometallic complexes.
This report applies the approach outlined in Scheme 14 to the
area of group 8 alkenyl chemistry.
Caulton,17 Hill,18 and others,19 as well as by ourselves.20 The
most convenient triphenylphosphine-stabilized alkenyl com-
plexes to use as starting materials are those of the forms
[Ru(CR1dCHR2)Cl(CO)(PPh3)2]13 and[Ru(CR1dCHR2)Cl(CO)-
(BTD)(PPh3)2] (BTD ) 2,1,3-benzothiadiazole),18a where BTD
is a labile ligand. A marked advantage of the latter is that it
avoids contamination with tris(phosphine) material. Reaction
of [Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2] with the pip-
erazine dithiocarbamate S2CNC4H8NH2 yielded the cation
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1). The
retention of the enynyl ligand was indicated by a broadened
singlet resonance for Hꢀ at 6.29 ppm in the 1H NMR spectrum,
while peaks for the piperazine protons were seen at 2.59 and
3.49 ppm. Resonances for the NH2 protons were not generally
observed and were assumed to be broad and/or obscured by
other resonances. Three characteristic bands were visible in the
solid-state infrared spectrum (KBr/Nujol) for the νCdC, νCO, and
νCS absorptions at 2148, 1924, and 999 cm-1, respectively. A
mutually trans disposition of phosphines was indicated by a
singlet in the 31P NMR spectrum at 38.0 ppm. A molecular ion
at m/z 1018 and satisfactory elemental analysis confirmed the
overall composition of the compound. The particularly advanta-
Results and Discussion
A wide range of ruthenium alkenyl complexes11 is readily
accessible from hydrometalation of alkynes by the compounds
[RuHCl(CO)L2/3] (L ) PiPr3,12 PPh313), and many aspects of
the resulting alkenyl complexes have been explored in funda-
mental work by the groups of Werner,14 Esteruelas,15 Santos,16
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1
geous spectroscopic features of the enynyl ligand (Hꢀ in H
NMR, νCdC in IR) led to complex 1 being employed as the
primary starting point for the multimetallic complexes described
here. To complete the characterization of the compound, single
crystals were grown and a structural study undertaken (Figure
1):
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Wang, M.; Honarkhah, S. J.; Tocher, D. A. Inorg. Chim. Acta 2005, 358,
3218–3226.

200 Organometallics, Vol. 28, No. 1, 2009
Macgregor et al.
Further examples of symmetrical bimetallic species were
prepared using the direct method outlined above. Reaction of 2
equiv of [Ru(CHdCHBut)Cl(CO)(PPh3)2] with KS2CNC4H8-
NCS2K (Scheme 4) led to the formation of
[{Ru(CHdCHBut)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (3). A new
carbonyl absorption was observed at 1908 cm-1 in the solution
infrared spectrum (CH2Cl2) and a new singlet in the 31P NMR
spectrum at 40.4 ppm. The retention of the alkenyl ligand was
evidenced by a singlet at 0.02 ppm for the methyl protons in
1
the H NMR spectrum along with a doublet resonance for Hꢀ
at 5.95 ppm (JHH ) 17.3 Hz). The piperazine protons gave rise
to a broad series of multiplets between 1.99 and 2.60 ppm. This
dynamic behavior, presumably as a result of flexing of the
piperazine ring, could not be frozen out at low temperatures
(-40 °C) and coalesced to some extent at elevated temperatures
(+40 °C). High-molecular-weight complexes often fail to yield
a molecular ion in the mass spectrum, and this was found to be
the case with complex 3: only fragmentations for loss of a
alkenyl ligand and [M - alkenyl - PPh3]+ were found at m/z
1631 and 1367, respectively. The formulation was supported
by elemental analysis, which was found to be in good agreement
with calculated values. The complex [{Ru(CHdCHC6H4Me-
4)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (4) was prepared in an
identical manner.
Figure 1. Molecular structure of the cation in compound 1. Selected
bond distances (Å) and angles (deg): Ru1-C1 ) 1.831(5),
Ru1-C12 ) 2.109(5), Ru1-S2 ) 2.466(1), Ru1-S1 ) 2.508(1),
O1-C1 ) 1.166(6), S1-C2 ) 1.707(5), S2-C2 ) 1.697(6),
N1-C2 ) 1.354(7), C11-C12 ) 1.351(7), C13-C14 ) 1.215(7);
S2-C2-S1 ) 114.6(3), S2-Ru1-S1 ) 70.33(4), C11-C12-Ru1
) 127.6(4), P1-Ru1-P2 ) 173.73(4), C(13)-C(14)-C(15) )
169.9(6).
Having prepared examples with both mono- and disubstituted
alkenyl ligands, we decided to explore complexes with alkenyl
moieties derived from propargyl alcohols (Scheme 4). The
species [Ru(CHdCHCPh2OH)(BTD)Cl(CO)(PPh3)2] was ob-
tained readily from the hydroruthenation of 1,1-diphenyl-2-
propyn-1-ol by [RuHCl(CO)(BTD)(PPh3)2]. This went on to
react in a manner similar to that for complex 4 to yield a
colorless product formulated as [{Ru(CHdCHCPh2OH)(CO)-
(PPh3)2}2(S2CNC4H8NCS2)] (5) on the basis of spectroscopic
and analytical data. Treatment of [Ru(CHdCHCO2Me)-
Cl(CO)(PPh3)2] with 0.5 equiv of KS2CNC4H8NCS2K yielded
[{Ru(CHdCHCO2Me)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (6). The
ester group was seen as a medium-intensity νCdO absorption at
1659 cm-1, to lower frequency of the more intense carbonyl
absorption at 1917 cm-1 in the solution (CH2Cl2) infrared
In both compounds the piperazine ring adopts a chair conforma-
tion. The Ru-S bond distances in compound 1 are slightly
longer than those in the bimetallic examples, while the C-S
and N-C distances are similar. However, the S2-Ru1-S1
angle of 70.33(4)° is smaller than that of 71.40(7)° in the
previously reported complex.
Successive treatment of 1 with triethylamine, carbon disulfide,
and [Ru(C(CdCPh)dCHPh)Cl(CO)(BTD)(PPh3)2] led to gen-
eration of the ammonium moiety and conversion into the
bimetallic complex [{Ru(C(CdCPh)dCHPh)(CO)(PPh3)2}2(S2-
CNC4H8NCS2)] (2), as shown in Scheme 3. The same product
was obtained by reaction of the double salt KS2CNC4H8NCS2K
with 2 equiv of [Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2].
As might be expected, compound 2 was found to display
spectroscopic features similar to those of 1 with a broadened
alkenyl resonance at 6.32 ppm and peaks between 2.21 and 2.27
ppm for the piperazine protons in the 1H NMR spectrum,
reflecting the different environments of the axial and equatorial
protons. Integration of the aromatic region confirmed the
presence of two Ru(PPh3)2(enynyl) units to one piperazine.
Absorptions were observed in the solid-state infrared spectrum
at 2153 (νCdC) and 1924 cm-1 (νCO), further indicating retention
of the enynyl and carbonyl ligands but failing to show any
significant change from the same features in the precursor. A
molecular ion in the FAB mass spectrum at m/z 1952 and good
agreement of elemental analysis with the calculated values
helped differentiate between compounds 1 and 2.
spectrum. The methyl protons were observed at 3.37 ppm in
1
the H NMR spectrum along with HR and Hꢀ at 9.47 (JHH
)
15.0 Hz) and 5.50 ppm, respectively.
In addition to the literature compounds employed, a number
of new alkenyl complexes were prepared for use in the project.
Reaction of HCt CHCH2OSiMe2But with [RuHCl(CO)(PPh3)3]
yielded a pale yellow product, formulated as the alkenyl complex
[Ru(CHdCHCH2OSiMe2But)Cl(CO)(PPh3)2] (7). Singlet reso-
1
nances in the H NMR spectrum for the methyl and tert-butyl
groups were observed at 0.15 and 0.78 ppm, respectively, along
with a doublet for the methylene protons at 3.85 coupled to the
Hꢀ proton (JHH ) 6.9 Hz). A doublet of triplets of triplets was
observed for Hꢀ at 4.82 ppm due to coupling with Hꢀ, the CH2
protons, and the phosphine nuclei, while the resonance arising
from HR appeared at 7.74 as a doublet of triplets.
Initially, the reaction mixture to transform 1 into 2 was stirred
for 2 h. However, the presence of side products was observed
and these were attributed to insertion of carbon disulfide into
the Ru-C bond, a reaction which has some precedent.21 The
reaction to form compound 2 is relatively rapid, and so best
results were obtained using a method in which the reaction
mixture was stirred only for 10 min before workup.
The silyl-substituted alkenyl complex
7 reacts with
KS2CNC4H8NCS2K to give the off-white product [{Ru(CHd
CHCH2OSiMe2But)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (8) in mod-
erate yield (Scheme 4). The resonances for the alkenyl
substituent proved particularly diagnostic, giving rise to singlets
at -0.22 (SiCH3) and 0.77 ppm (But) and a doublet at 3.44
ppm (CH2, JHH ) 5.8 Hz).
In order to increase the number of metals incorporated into
the system, ethynylferrocene was used to prepare the complexes
(21) Loumrhari, H.; Ros, J.; Yanez, R.; Torres, M. R. J. Organomet.
Chem. 1991, 408, 233–239.

Bi-, Tri-, and Tetrametallic Complexes of Ru(II) and Os(II)
Organometallics, Vol. 28, No. 1, 2009 201
Scheme 3. Two Routes to a Homobimetallic Ruthenium Speciesa
a
Legend: (i) S2CNC4H8NH2, NH4BF4; (ii) NEt3, CS2, [Ru(C(Ct CPh)dCHPh)Cl(CO)(BTD)(PPh3)2]; (iii) 0.5 equiv of KS2CNC4H8NCS2K.
Scheme 4. Direct Preparation of Homobimetallic Ruthenium and Osmium Speciesa
a
Legend: (i) 0.5 equiv of KS2CNC4H8NCS2K; L ) no ligand or BTD (2,1,3-benzothiadiazole).
[Ru(CHdCHFc)Cl(CO)(PPh3)2] (9)22 and [Os(CHdCHFc)Cl-
(PPh3)2] (alkenyl ) CHdCHC6H4Me-4, C(Ct CPh)dCHPh) in
the reactions with KS2CNC4H8NCS2K leads to the formation
of the yellow products [{Os(CHdCHC6H4Me-4)(CO)(PPh3)2}2-
(S2CNC4H8NCS2)] (12) and [{Os(C(Ct CPh)dCHPh)(CO)-
(PPh3)2}2(S2CNC4H8NCS2)] (13) in good to moderate yield
(Scheme 4). Spectroscopic and analytical features were similar
to those for the ruthenium analogues, with the exception of the
resonances in the 31P NMR spectrum at 8.3 (12) and 6.6 ppm
(13), which displayed a shift to higher field due to the greater
shielding afforded by the osmium centers. A molecular ion was
observed at m/z 1957 in the FAB mass spectrum of 12, and an
excellent agreement with calculated values was found for the
microanalytical data.
(CO)(BTD)(PPh3)2] (10) in good yield from reaction with
[RuHCl(CO)(PPh3)3] and [OsHCl(CO)(BTD(PPh3)2]. The pres-
ence of the ferrocenyl unit (in 9) was clearly indicated by
resonances at 3.78 (C5H5), 3.88 (C5H4), and 3.96 ppm (C5H4)
1
in the H NMR spectrum, while HR and Hꢀ protons resonated
as doublets (JHH ) 13.3 Hz) at 7.74 and 5.39 ppm.
Use of [Ru(CHdCHFc)Cl(CO)(PPh3)2] allows the introduc-
tion of a new carbon-bonded metal center into the system to
create the tetrametallic product [{Ru(CHdCHFc)(CO)(PPh3)2}2-
(S2CNC4H8NCS2)] (11) on reaction with KS2CNC4H8NCS2K
(Scheme 4). Again, a multiplet was observed for the piperazine
1
protons between 2.56 and 2.82 ppm in the H NMR spectrum,
while the ferrocenyl group gave rise to resonances slightly
shifted with respect to those in the precursor. Resonances for
HR and Hꢀ were observed at 7.70 and 5.84 ppm showing mutual
coupling of 15.6 Hz. Somewhat surprisingly, a molecular ion
was observed in the FAB mass spectrum at m/z 1967, albeit in
low abundance.
With the routes to symmetrical species well established, our
attention turned to exploring the wider potential of this
methodology to prepare unsymmetrical bimetallic species. Using
the complex [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)-
(PPh3)2]Cl (1) as the starting point due to the characteristic
features in its IR and 1H NMR spectra, the addition of different
alkenyl species was investigated. Treatment of 1 with triethy-
lamine and carbon disulfide followed by addition of [Ru(CHd
CHBut)Cl(CO)(BTD)(PPh3)2] led to the formation of a yellow-
brown product. Retention of the enynyl moiety was indicated
by the νCt C absorption at 2152 cm-1 in the solid-state infrared
While a number of linked bimetallic complexes of ruthenium
are known (Scheme 2), very few examples have been reported
for osmium. These are limited to the recently reported complexes
[OsCl(CO)(PPh3)2(PR3)(CHdCHC6H3(Ct CH-3)CHdCH)-
OsCl(CO)(PPh3)2(PR3)] (R ) Me, Ph) prepared by Jia and
co-workers10 and [OsCl(CO)(PPri3)2(CHdCH(CH2)4CHdCH)OsCl-
(CO)(PPri3)2] by the group of Esteruelas.23 Employing the
versatile osmium starting materials [Os(alkenyl)Cl(CO)(BTD)-
1
spectrum and a singlet resonance in the H NMR spectrum at
6.21 ppm. Only one broadened νCO absorption was observed in
the solution infrared spectrum (CH2Cl2) at 1912 cm-1, but
1
additional peaks in the H NMR spectrum at 0.34 (s, But) and
4.54 ppm (d, CHBut, JHH ) 16.4 Hz) indicated the presence of
the new metal unit. This was corroborated by two distinct
phosphorus environments in the 31P NMR spectrum at 38.0 and
(22) Wilson, D. J. M.Sc. Thesis, Imperial College, 1996.
(23) Esteruelas, M. A.; Lahoz, F. J.; Onate, E.; Oro, L. A.; Valero, C.;
Zeier, B. J. Am. Chem. Soc. 1995, 117, 7935–7942.

202 Organometallics, Vol. 28, No. 1, 2009
Macgregor et al.
Scheme 5. Preparation of Unsymmetrical Bimetallic
Ruthenium Speciesa
Scheme 6. Preparation of the Heterotrimetallic Group 8
Metal Complex 21a
a
Legend: (i) NEt3, CS2; (ii) [Ru(CHdCHR)Cl(CO)(BTD)(PPh3)2]
)
But (14), C6H4Me-4 (15), CPh2OH (16)), [Ru(CHd
a
(R
CHR)Cl(CO)(PPh3)2] (R
C5H4FeC5H5 (19)), or [Os(CHdCHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(20).
Legend: (i) S2CNC4H8NH2, NH4BF4; (ii) NEt3, CS2, [Os(CHdCHFc)-
)
CO2Me (17), CH2OSiMe2But (18),
Cl(CO)(BTD)(PPh3)2].
are represented. This was indeed achieved with the synthesis
of [{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Os-
(CHdCHFc)(CO)(PPh3)2}] (21) by the same route (Scheme 6).
Again, a broadened carbonyl absorption with a distinct shoulder
to lower frequency was observed in the solution IR spectrum
at 1927 cm-1 (different from that found for the starting material)
alongside a νCdC band at 2152 cm-1 and a new resonance at
7.9 ppm in the 31P NMR spectrum pointed to the successful
incorporation of the osmium unit. Typical resonances for the
enynyl and ferrocenyl alkenyl ligands confirmed their presence.
A peak assigned to loss of phosphine was identified at m/z 1784
in the FAB mass spectrum. Elemental analysis was found to
agree well with calculated values. Although the compound was
found to be reasonably microcrystalline, no crystals of sufficient
quality for a structural determination could be grown. Apart
from some cluster examples,25a to the best of our knowledge,
this FeRuOs species is only the second example of a complex
containing all three metals of the triad after the complex trans-
[(FcCt C)C6H3{Ct CRuCl(dppm)2}{Ct COsCl(dppm)2] re-
ported by Long and co-workers.25b Very recently, Lang and co-
workers have reported an elegant synthetic route to a heptametallic
complex containing the group 8 triad along with Ti, Re, Pt,
and Cu centers.25c
40.6 ppm. By comparison with the chemical shift of the starting
material, these were assigned to the Ru(PPh3)2 units bonded to
the enynyl and tertiarybutyl alkenyl ligands, respectively. A
fragment for loss of phosphine at m/z 1568 in the FAB mass
spectrum and elemental analysis confirmed the overall formula-
tionas[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHR)(CO)(PPh3)2}] (R ) But, 14).
In a similar manner (Scheme 5), further examples of
unsymmetrical bimetallics with units bearing monosubstituted
alkenyl ligands (R ) C6H4Me-4 (15), CPh2OH (16), CO2Me
(17), CH2OSiMe2But (18)) were prepared. These constitute the
first examples of unsymmetrical organometallic complexes
bridged by a dithiocarbamate linkage. Using [Ru(CHd
CHFc)Cl(CO)(PPh3)2](9),atrimetallicspecies,[{Ru(C(Ct CPh)d
CHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru(CHdCHFc)(CO)(P-
Ph3)2}] (19), was prepared from 1 in the same manner. In
addition to the peak at 37.8 ppm in the 31P NMR spectrum for
the enynyl end of the molecule, a new resonance at 39.3 ppm
was observed for the ferrocenyl alkenyl unit as well as typical
resonances in the 1H NMR spectrum, similar to those found in
9 and 11. The success of these reactions led to an attempt to
introduce a different metal center as the new end unit. The BTD
and chloride ligands in the complex [Os(CHdCHC6H4Me-
4)Cl(CO)(BTD)(PPh3)2] were readily displaced by the metal-
ladithiocarbamate [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NCS2)-
(CO)(PPh3)2][NHEt3], generated in situ, to yield the mixed-metal
Although the anionic metalladithiocarbamate [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NCS2) (CO)(PPh3)2]- was always gen-
erated in situ in the experiments outlined here, this species can
be characterized as the [HNEt3]+ salt on addition of NEt3 and
CS2 to a solution of compound 1 in dichloromethane followed
by precipitation with diethyl ether. The anion gave rise to two
species
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4-
H8NCS2){Os(CHdCHC6H4Me-4)(CO)(PPh3)2}] (20) in moder-
ate yield. This complex joins the species [RuCl(CO)-
(PPri3)2(CHdCH(CH2)4CHdCH)OsCl(CO)(PPri3)2] as one of
very few known ruthenium-osmium bimetallic compounds
bearing alkenyl ligands.24 As expected, a substantial difference
was observed in the chemical shift of the phosphorus nuclei
attached to the ruthenium (38.0 ppm) and osmium (8.1 ppm)
centers. Other spectroscopic features in the 1H NMR spectrum
were similar to those observed previously. A molecular ion was
clearly identifiable in the FAB mass spectrum at m/z 1953 along
with fragmentations due to loss of phosphine and a fragment
attributed to [M - PPh3 - alkenyl]+. Elemental analysis further
supported the above formulation.
1
piperazine environments in the H NMR spectrum at 2.44 and
4.02 ppm along with a resonance for Hꢀ at 6.29 ppm. The 31P
NMR resonance at 37.8 ppm is little changed from that of the
precursor 1. On standing in solution for more than 1 h, formation
of the symmetrical species 2 began to occur. This behavior has
been noted for the zwitterion [Ru(S2CNC4H8NCS2)(dppm)2].4
A subtle variation on the unsymmetrical systems described
above is the preparation of a bimetallic complex in which only
one coligand differs at each end. The thiocarbonyl analogues
of the alkenyl starting materials employed here are readily
accessible from hydroruthenation of [RuHCl(CS)(BTD)(PPh3)2]
or [RuHCl(CS)(PPh3)3].8 Accordingly, [Ru(C(Ct CPh)d-
CHPh)(S2CNC4H8NH2)(CS)(PPh3)2]Cl (22) was prepared from
[Ru(C(Ct CPh)dCHPh)Cl(CS)(PPh3)2] by the same method as
that used for 1. Spectroscopic features were essentially identical
These results opened up the exciting possibility of a complex
being accessible in which all three metals of the group 8 triad
(24) Buil, M.; Esteruelas, M. A. Organometallics 1999, 18, 1798–1800.
to those for 1 other than the νCS absorption at 1246 cm-1
.

Bi-, Tri-, and Tetrametallic Complexes of Ru(II) and Os(II)
Organometallics, Vol. 28, No. 1, 2009 203
Scheme 7. Preparation of a Bimetallic Ruthenium Species
(23) with both Carbonyl and Thiocarbonyl Ligandsa
Scheme 8. Preparation of a Bis(alkynyl)ruthenium Species
(24)a
t
a
Legend: (i) excess HC≡CBu , heat; R ) C6H4Me-4.
a
Legend: (i) NEt3, CS2, [Ru(C(Ct CPh)dCHPh)Cl(CO)(PPh3)2].
Attempts to record a potentially diagnostic 13C NMR spectrum
were defeated by persistent precipitation of the complex from
high concentration solutions over the period of data accumula-
tion, leading to a poor signal-to-noise ratio. The mass spectrum
failed to provide a molecular ion, only exhibiting a fragmenta-
tion attributed to m/z 1691 for loss of two phosphines and a
carbonyl ligand. However, elemental analysis was found to be
in excellent agreement with calculated values. Trimetallic
compounds of the heavier congeners of group 10 were also
prepared from PdCl2(NCMe)2 and PtCl2(NCPh)2 to yield
[{Ru(C(Ct CPh)dCHPh)(S2CNC4H8NCS2)(CO)(PPh3)2}2M] (M
) Pd, 26; M ) Pt, 27), respectively. Data for these complexes
were found to be similar to those exhibited by 25. The RuZnRu
Treatment of 22 with NEt3 and CS2 followed by addition of
[Ru(C(Ct CPh)dCHPh)Cl(CO)(PPh3)2] resulted in the forma-
tion (Scheme 7) of [{Ru(C(Ct CPh)dCHPh)(CO)-
(PPh3)2}(S2CNC4H8NCS2){Ru(C(Ct CPh)dCHPh)(CS)(PPh3)2}]
(23). As may be expected, multinuclear NMR spectroscopic
features for both ends of the molecule, though clearly broadened,
were so similar as to render them indistinguishable. However, a
shift of the νCS absorption to 1259 cm-1 and the presence of the
νCO band at 1920 cm-1 attested to the success of the reaction. A
very broad 31P NMR resonance centered at 34.1 ppm was observed,
while fragmentation for [M - PPh3]+ at m/z 1702 and satisfactory
elemental analysis supported the formulation as that above.
The examples above have illustrated the versatility of the
piperazine dithiocarbamate linkage in the synthesis of diverse
symmetrical and unsymmetrical organometallic compounds. The
next challenge was to explore the ability of this ligand to support
functional group transformations of the σ-bonded organic
ligands. Treatment of the symmetrical tolyl-substituted alkenyl
complex [{Ru(CHdCHC6H4Me-4)(CO)(PPh3)2}2(S2CNC4H8-
NCS2)] (4) with an excess of HCt CBut in refluxing toluene
resulted in a tan product which displayed a νCO absorption in
the solid-state infrared spectrum at 1947 cm-1 along with a
completely new band at 2102 cm-1 in the region typical of
complex
[{Ru(C(Ct CPh)dCHPh)(S2CNC4H8NCS2)(CO)-
(PPh3)2}2Zn] (28) was synthesized in a similar manner from 1
with NEt3, CS2, and zinc acetate to provide a group 12 example.
While a square-planar geometry around the d8 group 10 metals
in 25-27 is assumed, the Zn(II) (d10) center in 28 is likely to
adopt a tetrahedral arrangement.
Conclusion
The methodology described above illustrates how the pip-
erazine dithiocarbamate system can be used to link a range of
organometallic centers. The accessibility of unsymmetrical
systems via this route is particularly significant, as this is often
impossible to achieve using conventional bifunctional linkages.
Furthermore, the robust nature of the bis(dithiocarbamate) linker
has been illustrated by a successful functional group transforma-
tion performed on a bimetallic complex, converting a dialkenyl
compound into one bearing alkynyl ligands. The tri- and
tetrametallic species prepared further illustrate the flexibility of
the approach, allowing metal units to function as the connecting
moiety between ruthenium alkenyl complexes. The potential of
this idea, illustrated here by four-coordinate group 10 and 12
metals, will now be explored using units based on d- and f-block
metals capable of chelating a greater number of dithiocarbamate
ligands in order to expand the geometrical possibilities of the
linkage metal atom.
1
alkynyl νCdC bands. In the H NMR spectrum, no AB system
was observed for a tolyl group or HR or Hꢀ protons. Instead, a
singlet integrating to 18 protons was observed at 0.94 ppm. The
MALDI mass spectrum showed a peak at m/z 1706 correspond-
ing to the molecular ion for the alkynyl complex
[{Ru(Ct CBut)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (24) along with
further fragmentations from loss of carbonyl and phosphine
ligands (Scheme 8). Two closely separated peaks were observed
in the room temperature 31P NMR spectrum at 38.9 and 39.3
ppm, indicating slightly different environments for the two metal
units, which coalesced on warming.
An alternative route to trimetallic complexes was also
explored using metal precursors of groups 10 and 12 (Scheme
9), which are well-known to form bis(dithiocarbamate) species.
Sequential treatment of
2
equiv of [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1) with excess
triethylamine and carbon disulfide followed by 1 equiv of
Ni(OAc)2 led to a yellow product in low yield. As might be
expected, the spectroscopic features for the desired complex
[{Ru(C(Ct CPh)dCHPh)(S2CNC4H8NCS2)(CO)(PPh3)2}2Ni]
(25) were found to be very similar to those of 1. IN comparison
to the same feature in 1, a slight shift was observed for Hꢀ in
the 1H NMR spectrum to 6.30 ppm and the piperazine protons
were spread over a slightly greater range of chemical shifts.
Experimental Section
General Comments. All experiments were carried out under
aerobic conditions, and the majority of the complexes appear to be
indefinitely stable toward the atmosphere in solution or in the solid
state. Solvents were used as received from commercial sources. The
following complexes have been described elsewhere: [RuHCl(CO)(P-

204 Organometallics, Vol. 28, No. 1, 2009
Scheme 9. Preparation of Ru2M Heterotrimetallic Speciesa
Macgregor et al.
a
Legend: (i) NEt3, CS2; (ii) Ni(OAc)2, PdCl2(NCMe)2, PtCl2(NCPh)2 or Zn(OAc)2; M ) Ni (25), Pd (26), Pt (27), Zn (28).
Ph3)3],26 [RuHCl(CO)(BTD)(PPh3)2],27 [OsHCl(CO)(BTD)(PPh3)2],18h
1245, 1203, 999 (νC-S) cm-1. 1H NMR: δ 2.59 (s, 4 H, NC4H8N),
3.49 (s, 4 H, NC4H8N), 6.29 (s, 1 H, Hꢀ), 6.94-7.57 (m, 40 H,
C6H5) ppm. 13C NMR (CD2Cl2): δ 41.4-42.1 (m, NC4H8N), 102.1,
98.4 (s × 2, Ct C), 124.5-140.77 (m, C6H5), 126.4 (s, dCH), 146.6
NMR: δ 38.0 (s, PPh3) ppm. MS (FAB): m/z (%) 1018 (18) [M]+,
857 (10) [M - S2CNC4H8NH2]+, 815 (20) [M - alkenyl]+, 728
(56) [M - CO - PPh3]+. Anal. Found: C, 66.0; H, 4.9; N, 2.6.
Calcd for C58H51ClN2OP2RuS2: C, 66.1; H, 4.9; N, 2.7.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (2).
(a) KS2CNC4H8NCS2K (35 mg, 0.111 mmol) was dissolved in
MeOH (15 cm3) and water (2 cm3), and [Ru(C(Ct
CPh)dCHPh)Cl(CO)(PPh3)2] (200 mg, 0.224 mmol) was added in
dichloromethane (25 cm3). After the mixture was stirred at room
temperature for 20 min, the solvent volume was reduced by rotary
evaporation. The pale yellow product was filtered off, washed with
water (5 cm3), ethanol (10 cm3), and hexane (10 cm3), and dried
under vacuum. Yield: 170 mg (78%).
[RuHCl(CS)(PPh3)3],28 [Ru(CR1dCHR2)Cl(CO)(PPh3)2] (R1 ) H, R2
)
But,16h CO2Me16i and R1 Ct CPh, R2 Ph18a,b),
) )
[Ru(CR1dCHR2)Cl(CO)(BTD)(PPh3)2] (R1 ) H, R2 ) C6H4Me-4,
CPh2OH),18c [Os(CR1dCHR2)Cl(CO)(BTD)(PPh3)2] (R1 ) H, R2 )
C6H4Me-4; R1 ) Ct CPh, R2 ) Ph),18h [PdCl2(NCMe)2],29
[PtCl2(NCPh)2],30 [S2CNC4H8NH2],4,31 and [KS2CNC4H8NCS2K].32
MALDI-MS and FAB-MS data were obtained using Micromass
TofSpec and Autospec Q instruments, respectively. The FAB mass
spectrum for 15 was obtained at the EPSRC National Mass Spec-
trometry Service Center, University of Wales Swansea. Infrared data
were obtained using a Perkin-Elmer Paragon 1000 FT-IR spectrometer,
KBr plates were used for solid-state IR spectroscopy, and characteristic
phosphine-associated infrared data are not reported. NMR spectroscopy
was performed at 25 °C using Varian Mercury 300 or Varian Unity
500 (for complex 7) spectrometers in CDCl3 unless otherwise indicated.
All couplings are in hertz, and 31P NMR spectra are proton-decoupled.
Elemental analysis data were obtained from London Metropolitan
University. 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 the 1H NMR spectrum.
[Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NH2)]Cl (1).
The reagent [S2CNC4H8NH2] (220 mg, 1.356 mmol) was dissolved
in methanol (20 cm3) and the complex [Ru(C(Ct CPh)d
CHPh)Cl(CO)(PPh3)2] (1000 mg, 1.121 mmol) was added in
dichloromethane (60 cm3). After the mixture was stirred at room
temperature for 3 h, the volatiles were removed. The crude product
was dissolved in a small amount of dichloromethane, and ethanol
(20 cm3) was added. Slow concentration under reduced pressure
gave a yellow product, which was filtered off, washed with hexane
(10 cm3), and dried under vacuum. Yield: 820 mg (69%). The BTD
analogue of the starting material can also be used to give a
comparable yield of compound 1. IR (CH2Cl2): 2153 (νCt C), 1927
(νCO) cm-1. IR (Nujol): 2148 (νCt C), 1924 (νCO), 1592, 1311, 1267,
(s, RuCd), 197.3 (t, CO, JPC ) 17.7 Hz), 207.7 (s, CS2) ppm. 31
P
(b) [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (100
mg, 0.095 mmol) was dissolved in dichloromethane (15 cm3) and
treated with NEt3 (5 drops, excess) and CS2 (5 drops, excess)
followed by
a
dichloromethane solution (10 cm3) of
[Ru(C(Ct CPh)dCHPh)Cl(CO)(PPh3)2] (85 mg, 0.095 mmol).
After the mixture was stirred at room temperature for 20 min, the
solvent volume was reduced by rotary evaporation. The pale yellow
product was filtered off, washed with water (5 cm3), ethanol (10
cm3), and hexane (10 cm3), and dried under vacuum. Yield: 135
mg (73%). IR (CH2Cl2): 2144 (νCt C), 1915 (νCO) cm-1. IR (Nujol):
2153 (νCt C), 1924 (νCO), 1591, 1277, 1212, 1161, 1000 (νC-S) cm-1
.
1H NMR (C6D6): δ 2.21-2.27 (m, 8 H, NC4H8N), 6.32 (s, 2 H,
Hꢀ), 6.51-7.48 (m, 80 H, C6H5) ppm. 31P NMR: δ 38.3 (s, PPh3)
ppm. MS (FAB): m/z (%) 1952 (2) [M]+, 1689 (1) [M - PPh3]+,
1485 (3) [M - PPh3 - alkenyl]+. Anal. Found: C, 67.9; H, 4.6; N,
1.5. Calcd for C112H90N2O2P4Ru2S4 · 0.5CH2Cl2: C, 67.8; H, 4.6;
N, 1.4.
[{Ru(CHdCHBut)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (3). KS2-
CNC4H8NCS2K (20 mg, 0.064 mmol) was dissolved in MeOH (10
cm3), and the complex [Ru(CHdCHBut)Cl(CO)(PPh3)2] (100 mg,
0.129 mmol) was added in dichloromethane (15 cm3). After the
mixture was stirred at room temperature for 20 min, all solvent
was removed by rotary evaporation. The product was taken up in
a small amount of dichloromethane and filtered through diatoma-
ceous earth. Ethanol (15 cm3) was added, and a pale brown powder
was obtained after concentration under reduced pressure. The
product was filtered off, washed with ethanol (10 cm3) and hexane
(10 cm3), and dried under vacuum. Yield: 64 mg (58%). IR
(CH2Cl2): 1908 (νCO) cm-1. IR (Nujol): 1911 (νCO), 1731, 1601,
(25) (a) Hunstock, E.; Calhorda, M. J.; Hirva, P.; Pakkanen, T. A.
Organometallics 2000, 19, 4624–4628. (b) Long, N. J.; Martin, A. J.; White,
A. J. P.; Williams, D. J.; Fontani, M.; Laschi, F.; Zanello, P. Dalton Trans.
2000, 3387–3392. (c) Packheiser, R.; Ecorchard, P.; Ru¨ffer, T.; Lang, H.
Organometallics,in press.
(26) Laing, K. R.; Roper, W. R. J. Chem. Soc. A 1970, 2149, 2153.
(27) Procedure modified substituting BTD for BSD from: Alcock, N. W.;
Hill, A. F.; Roe, M. S. J. Chem. Soc., Dalton Trans. 1990, 1737–1740.
(28) Brothers, P. J.; Roper, W. R. J. Organomet. Chem. 1983, 258, 73–
79.
(29) Andrews, M. A.; Chang, T. C.-T.; Cheng, C.-W. F.; Emge, T. J.;
Kelly, K. P.; Koetzle, T. F. J. Am. Chem. Soc. 1984, 106, 5913–5920.
(30) Fraccarollo, D.; Bertani, R.; Mozzon, M.; Belluco, U.; Michelin,
R. A. Inorg. Chim. Acta 1992, 201, 15–22.
(31) Dunderdale, J.; Watkins, T. A. Chem. Ind. (London) 1956, 174,
175.
1580, 1272, 1122, 1040, 999 (νC-S) cm-1. 1H NMR: δ 0.02 (s, 18
3
H, But), 1.99-2.60 (m, 8 H, NC4H8N), 5.95 (d, 2 H, Hꢀ, JHH
)
17.3 Hz), 6.92-7.34 (m, 60 H + 2 H, C6H5 + HR) ppm. 31P NMR:
δ 40.4 (s, PPh3) ppm. MS (FAB): m/z (%) 1631 (1) [M - alkenyl]+,
(32) Tombeux, J.; van Poucke, L. C.; Eeckhaut, Z. Spectrochim. Acta
1972, 28A, 1943–1947.

Bi-, Tri-, and Tetrametallic Complexes of Ru(II) and Os(II)
Organometallics, Vol. 28, No. 1, 2009 205
1
1367 (2) [M - alkenyl - PPh3]+. Anal. Found: C, 64.7; H, 5.2; N,
(νC-S) cm-1. H NMR: δ -0.22 (s, 12 H, SiCH3), 0.77 (s, 18 H,
But), 2.52-2.84 (m, 8 H, NC4H8N), 3.44 (d, 2 H, CH2, 3JHH ) 5.8
Hz), 4.91 (m, 2 H, Hꢀ), 6.77 (m, 2H, HR), 7.26-7.54 (m, 60 H,
C6H5) ppm. 31P NMR: δ 40.0 (s, PPh3) ppm. MS (FAB): m/z (%)
1453 (3) [M - PPh3 - alkenyl]+. Anal. Found: C, 61.5; H, 5.6; N,
1.5. Calcd for C98H106N2O4P4Ru2S4Si2 · 0.5CH2Cl2: C, 61.3; H, 5.6;
N, 1.5.
1.8. Calcd for C92H90N2O2P4Ru2S4: C, 64.6; H, 5.3; N, 1.6.
[{Ru(CHdCHC6H4Me-4)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (4).
This compound was prepared as for the synthesis of 3 using
KS2CNC4H8NCS2K (29 mg, 0.092 mmol) and [Ru(CHdCHC6H4Me-
4)Cl(CO)(PPh3)2] (150 mg, 0.186 mmol) to provide a pale yellow
powder. Yield: 98 mg (59%). IR (CH2Cl2): 1916 (νCO) cm-1. IR
(Nujol): 1919 (νCO), 1659, 1279, 1213, 1117, 999 (νC-S) cm-1
.
[Ru(CHdCHFc)Cl(CO)(PPh3)2] (9). The complex [RuHCl(CO)(P-
Ph3)3] (500 mg, 0.525 mmol) was dissolved in dichloromethane
(40 cm3) and ethanol (20 cm3). HCt CFc (120 mg, 0.571 mmol)
was added and the reaction mixture stirred for 2 h, and then more
ethanol (15 cm3) was added. On slow concentration under reduced
pressure a brown powder precipitated, which was filtered off,
washed with hexane (10 cm3), and dried under vacuum. Yield: 340
mg (68%). IR (CH2Cl2): 2036, 1933 (νCO), 1574 cm-1. IR (Nujol):
2026, 1925 (νCO), 1568, 1163, 1029, 969, 932, 820 cm-1. 1H NMR:
δ 3.78 (s, 5 H, C5H5), 3.88 (s(br), 2 H, C5H4), 3.96 (s, 2 H, C5H4),
1
NMR H: δ 2.21 (s, 6 H, CH3), 2.68 - 2.94 (m, 8 H, NC4H8N),
3
5.57 (d, 2 H, Hꢀ, JHH ) 15.9 Hz), 6.36, 6.80 ((AB)2, 8 H, C6H4,
JAB ) 7.9 Hz), 7.27 - 7.51 (m, 60 H, C6H5), 7.69 (d, 2 H, HR,
3JHH ) 16.0 Hz) ppm. 31P NMR: δ 39.7 (s, PPh3) ppm. MS
(MALDI): m/z (%) 1518 (1) [M - PPh3]+, 1374 (1) [M - PPh3 -
alkenyl - CO]+, 1258 (2) [M - 2PPh3]+. Anal. Found: C, 66.3;
H, 4.8; N, 1.5. Calcd for C98H86N2O2P4Ru2S4: C, 66.2; H, 4.9; N,
1.6.
[{Ru(CHdCHCPh2OH)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (5).
This compound was prepared as for the synthesis of 3 using
KS2CNC4H8NCS2K (15 mg, 0.048 mmol) and [Ru(CHd
CHCPh2OH)(BTD)Cl(CO)(PPh3)2] (100 mg, 0.097 mmol) to pro-
vide a colorless powder. Yield: 43 mg (45%). IR (CH2Cl2): 1901
3
5.39 (d, 1 H, Hꢀ, JHH ) 13.3 Hz), 7.37-7.54 (m, 30 H, C6H5),
7.74 (d, 1 H, HR, 3JHH ) 13.3 Hz) ppm. 31P NMR: δ 29.6 (s, PPh3)
ppm. MS (ES): m/z (%) 865 (100) [M - Cl]+. Anal. Found: C,
65.3; H, 4.3. Calcd for C49H41ClFeOP2Ru: C, 65.4; H, 4.6.
[Os(CHdCHFc)Cl(CO)(BTD)(PPh3)2] (10). This compound was
prepared as for the synthesis of 9 using [OsHCl(CO)(BTD)(PPh3)2]
(500 mg, 0.546 mmol) and HCt CFc (126 mg, 0.600 mmol) to
provide a dark purple product. Yield: 510 mg (83%). IR (CH2Cl2):
2022, 1906 (νCO) cm-1. IR (Nujol): 2022, 1910 (νCO), 1574, 1537,
(νCO) cm-1. IR (Nujol): 1914 (νCO), 1279, 1213, 1000 (νC-S) cm-1
.
1H NMR (CD2Cl2): δ 2.26-2.91 (m, 8 H, NC4H8N), 6.66 (m, 2 H,
Hꢀ), 7.30 - 7.50 (m, 80 H + 2 H, C6H5 + HR), (OH not observed)
ppm. 31P NMR: δ 41.5 (s, PPh3) ppm. MS (FAB, MALDI): not
diagnostic. Anal. Found: C, 66.8; H, 5.6; N, 1.5. Calcd for
1096, 954, 827, 746, 701 cm-1. H NMR (C6D6): δ 3.95 (s, 5 H,
1
C
110H112N2O4P4Ru2S4: C, 66.7; H, 5.7; N, 1.4.
C5H5), 4.08 (s(br), 2 H, C5H4), 4.30 (s(br), 2 H, C5H4), 6.28 (d, 1
H, Hꢀ, 3JHH ) 15.5 Hz), 6.80-7.69 (m, 30 H + 4 H, C6H5 + C6H4),
9.05 (d, 1 H, HR, 3JHH ) 15.5 Hz) ppm. 31P NMR: δ -3.0 (s, PPh3)
ppm. MS (ES): not diagnostic. Anal. Found: C, 58.6; H, 4.1; N,
2.2. Calcd for C55H45ClFeN2OOsP2S: C, 58.7; H, 4.0; N, 2.5.
[{Ru(CHdCHFc)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (11). This com-
[{Ru(CHdCHCO2Me)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (6). KS2-
CNC4H8NCS2K (16 mg, 0.051 mmol) was dissolved in MeOH (10
cm3) and [Ru(CHdCHCO2Me)Cl(CO)(PPh3)2] (80 mg, 0.103
mmol) was added in dichloromethane (20 cm3). After the mixture
was stirred at room temperature for 20 min, the solvent volume
was reduced by rotary evaporation, and the resulting white powder
was filtered off, washed with ethanol (10 cm3) and hexane (10 cm3),
and dried under vacuum. Yield: 60 mg (68%). IR (CH2Cl2): 1917
(νCO), 1659 (νCdO) cm-1. IR (Nujol): 1927 (νCO), 1698, 1678 (νCdO),
1534, 1278, 1250, 1214, 1147, 999 (νC-S), 911, 832 cm-1. 1H NMR:
δ 2.54-2.76 (m, 8 H, NC4H8N), 3.37 (s, 6 H, CH3), 5.50 (d, 2 H,
Hꢀ,3JHH ) 15.0 Hz), 7.26-7.47 (m, 60 H, C6H5), 9.47 (d, 2 H, HR,
3JHH ) 15.0 Hz) ppm. 31P NMR: δ 39.4 (s(br), PPh3) ppm. MS
(MALDI): m/z (%) 1574 (2) [M - alkenyl - 2CO]+, 1399 (6) [M
- PPh3 - 2CO]+, 1313 (20) [M - alkenyl - PPh3 - 2CO]+. Anal.
Found: C, 61.8; H, 4.5; N, 1.6. Calcd for C88H78N2O6P4Ru2S4: C,
61.7; H, 4.6; N, 1.6.
pound was prepared as for the synthesis of
KS2CNC4H8NCS2K (9 mg, 0.029 mmol) and [Ru(CHdCHFc)-
6 using
Cl(CO)(PPh3)2] (9; 50 mg, 0.056 mmol) to yield a light brown
powder. Yield: 42 mg (76%). IR (CH2Cl2): 2029, 1913 (νCO) cm-1
.
.
IR (Nujol): 2025, 1916 (νCO), 1213, 1027, 999 (νC-S), 812 cm-1
1H NMR (C6D6): δ 2.56-2.82 (m, 8 H, NC4H8N), 3.89 (s(br), 4
H, C5H4), 3.95 (s(br), 4 H, C5H4), 3.97 (s, 10 H, Cp), 5.84 (d, 2 H,
3
Hꢀ, JHH ) 15.6 Hz), 6.97-7.87 (m, 60 H, C6H5), 7.70 (dt, 2 H,
HR, JHH ) 15.6 Hz, JHP unresolved) ppm. 31P NMR: δ 39.8 (s,
3
PPh3) ppm. MS (FAB): m/z (%) 1967 (2) [M]+, 1705 (2) [M -
PPh3]+, 1443 (1) [M - 2PPh3]+. Anal. Found: C, 61.1; H, 4.4; N,
1.6. Calcd for C104H90Fe2N2O2P4Ru2S4 · CH2Cl2: C, 61.5; H, 4.5;
N, 1.4.
[Ru(CHdCHCH2OSiMe2But)Cl(CO)(PPh3)2] (7). The complex
[RuHCl(CO)(PPh3)3] (1000 mg, 1.050 mmol) was dissolved in
dichloromethane (70 cm3), and HCt CHCH2OSiMe2But (360 mg,
2.101 mmol) was added. After the mixture was stirred at room
temperature for 1 h, ethanol (40 cm3) was added. On slow
concentration under reduced pressure a pale yellow powder formed,
which was filtered off, washed with ethanol (20 cm3) and hexane
(10 cm3), and dried under vacuum. Yield: 660 mg (73%). IR
(CH2Cl2): 1933 (νCO), 1586 cm-1. IR (Nujol): 1933 (νCO), 1732,
[{Os(CHdCHC6H4Me-4)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (12).
This compound was prepared as for the synthesis of 3 using
KS2CNC4H8NCS2K (15 mg, 0.048 mmol) and [Os(CHdCHC6H4Me-
4)Cl(BTD)(CO)(PPh3)2] (100 mg, 0.097 mmol) to yield a yellow
powder. Yield: 83 mg (88%). IR (CH2Cl2): 1898 (νCO) cm-1. IR
(Nujol): 1901 (νCO), 1279, 1216, 1027, 999 (νC-S), 950, 840 cm-1
.
1H NMR: δ 2.20 (s, 6 H, CH3), 2.62-2.97 (m, 8 H, NC4H8N),
3
1
1583, 1287, 1271, 1122, 1039, 836 cm-1. H NMR (CD2Cl2): δ
5.58 (d, 2 H, Hꢀ, JHH ) 15.0 Hz), 6.38, 6.80 ((AB)2, 8 H, C6H4,
JAB ) 6.0 Hz), 7.33-7.80 (m, 60 H, C6H5), 8.31 (d, 2 H, HR, 3JHH
) 15.0 Hz) ppm. 31P NMR: δ 8.3 (s, PPh3) ppm. MS (FAB): m/z
(%) 1957 (1) [M]+, 1697 (1) [M - PPh3]+. Anal. Found: C, 60.3;
H, 4.3; N, 1.5. Calcd for C98H86N2O2P4Ru2S4: C, 60.2; H, 4.4; N,
1.4.
0.15 (s, 6 H, SiCH3), 0.78 (s, 9 H, But), 3.85 (d, 2 H, CH2, JH H
3
ꢀ
3
3
) 6.9 Hz), 4.82 (dtt, 1 H, Hꢀ, JH H ) 12.2 Hz, JHH ) 6.9 Hz,
4JPH ) 2.0 Hz), 7.31-7.68 (m, 30 ꢀH, C6H5), 7.74 (dt, 1 H, HR,
R
ꢀ
ꢀ
3JH H ) 12.2 Hz, 3JPH unresolved) ppm. 31P NMR: δ 30.2 (s, PPh3)
ppm.ꢀMS (ES): m/z (%) 825 (5) [M - Cl]+, 563 (95) [M - Cl -
PPh3]+. Anal. Found: C, 64.3; H, 5.6. Calcd for C46H49ClO2P2RuSi:
C, 64.2; H, 5.7.
R
R
[{Os(C(Ct CPh)dCHPh)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (13).
KS2CNC4H8NCS2K (14 mg, 0.045 mmol) was dissolved in MeOH
(15 cm3), and the complex [Os(C(Ct CPh)dCHPh)Cl-
(BTD)(CO)(PPh3)2] (100 mg, 0.089 mmol) was added in dichlo-
romethane (20 cm3). After the mixture was stirred at room
temperature for 20 min, the solvent was removed by rotary
evaporation. The crude product was not sufficiently soluble, and
so after trituration in ethanol the yellow product was filtered off,
[{Ru(CHdCHCH2OSiMe2But)(CO)(PPh3)2}2(S2CNC4H8NCS2)]
(8). This compound was prepared as for the synthesis of 6 using
KS2CNC4H8NCS2K (18 mg, 0.057 mmol) and [Ru(CHd
CHCH2OSiMe2But)Cl(CO)(PPh3)2] (7; 100 mg, 0.116 mmol) to
yield an off-white powder. Yield: 60 mg (55%). IR (CH2Cl2): 1914
(νCO) cm-1. IR (Nujol): 1915 (νCO), 1572, 1252, 1213, 1029, 999

206 Organometallics, Vol. 28, No. 1, 2009
Macgregor et al.
washed with ethanol (10 cm3) and hexane (10 cm3), and dried under
mmol), triethylamine (4 drops, excess), CS2 (2 drops, excess), and
[Ru(CHdCHCO2Me)Cl(CO)(PPh3)2] (73 mg, 0.094 mmol) to give
an olive green product. Yield: 102 mg (59%). IR (CH2Cl2): 2152
(νCt C), 1926 (νCO) 1692, 1670 (νCdO) cm-1. IR (Nujol): 2152 (νCt C),
1922 (νCO), 1694, 1678 (νCdO), 1278, 1214, 999 (νC-S), 911, 831
vacuum. Yield: 90 mg (95%). IR (CH2Cl2): 2152 (νCt C), 1902 (νCO
)
cm-1. IR (Nujol): 2154 (νCt C), 1905 (νCO), 1592, 1215, 999 (νC-S),
1
948 cm-1. H NMR: δ 2.02-2.78 (m, 8 H, NC4H8N), 6.32 (s(br),
2 H, Hꢀ), 6.88-7.54 (m, 70 H, C6H5) ppm. 31P NMR: δ 6.6 (s,
PPh3) ppm. MS (FAB) not diagnostic. Anal. Found: C, 63.0; H,
4.6; N, 1.2. Calcd for C112H90N2O2Os2P4S4: C, 63.2; H, 4.3; N, 1.3.
1
cm-1. H NMR (CD2Cl2): δ 2.20-2.97 (m, 8 H, NC4H8N), 3.21
(s, 3 H, CH3), 5.41 (d, 1 H, dCHCO2Me, JHH ) 16.1 Hz), 6.21
(s(br), 1 H, dCHPh), 6.92-7.63 (m, 70 H, C6H5), 9.35 (d, 1 H,
RuCH, JHH ) 16.1 Hz) ppm. 31P NMR: δ 37.8 (s, PPh3,
Ru-enynyl), 39.4 (s, PPh3, Ru-CHdCHCO2Me) ppm. MS (FAB):
m/z (%) 1834 (1) [M]+, 1570 (1) [M - PPh3], 1484 (2) [M - PPh3
- alkenyl]. Anal. Found: C, 65.5; H, 4.7; N, 1.7. Calcd for
C100H84N2O4P4Ru2S4: C, 65.6; H, 4.6; N, 1.5.
{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHBut)(CO)(PPh3)2}] (14). A dichloromethane (20 cm3)
solution of [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl
(1; 150 mg, 0.142 mmol) was treated with triethylamine (4 drops,
excess) and CS2 (4 drops, excess). After the mixture was stirred
for 5 min, [Ru(CHdCHBut)Cl(BTD)(CO)(PPh3)2] (129 mg, 0.142
mmol) in dichloromethane (15 cm3) was added and this mixture
was stirred for 15 min and then filtered through diatomaceous earth.
Ethanol (15 cm3) was added, and a yellow-brown powder was
obtained by concentration under reduced pressure. It was filtered
off, washed with hexane (15 cm3), and dried under vacuum. Yield:
170 mg (65%). IR (CH2Cl2): 2152 (νCt C), 1912 (νCO) cm-1. IR
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHCH2OSiMe2But)(CO)(PPh3)2}] (18). This compound was
prepared as for the synthesis of 14 using [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 100 mg, 0.095
mmol), triethylamine (4 drops, excess), CS2 (2 drops, excess), and
[Ru(CHdCHCH2OSiMe2But)Cl(CO)(PPh3)2] (7; 82 mg, 0.095
mmol) to yield a yellow-green product. Yield: 110 mg (60%). IR
(CH2Cl2): 2153 (νCt C), 1920 (νCO) cm-1. IR (Nujol): 2147 (νCt C),
1917 (νCO), 1591, 1213, 999 (νC-S), 891 cm-1. 1H NMR: δ -0.18,
(s, 6 H, CH3), 0.74 (s, 9 H, But), 2.16 - 3.14 (m, 8 H, NC4H8N),
3.46 (s(br), 2 H, CH2), 4.92 (m, 1 H, dCHCO), 6.25 (s(br), 1 H,
dCHPh), 6.76 (m, 1 H, RuCH), 6.92-7.55 (m, 70 H, C6H5) ppm.
31P NMR: δ 37.7 (s, PPh3, Ru-enynyl), 40.1 (s, PPh3, Ru-alkenylSi)
ppm. MS (FAB): m/z (%) 1890 (1) [M - CO]+, 1390 (2) [M -
2PPh3]+. Anal. Found: C, 65.5; H, 5.1; N, 1.4. Calcd for
C105H98N2O3P4Ru2S4Si: C, 65.7; H, 5.2; N, 1.5.
(Nujol): 2152 (νCt C), 1916 (νCO), 1596, 1279, 1213, 999 (νC-S
)
1
cm-1. H NMR (C6D6): δ 0.34 (s, 9 H, But), 2.42-2.92 (m, 8 H,
3
NC4H8N), 4.54 (d, 1 H, dCHBut, JHH ) 16.4 Hz), 6.21 (s(br), 1
H, dCHPh), 6.28 (d, 1 H, RuCH, 3JHH ) 16.5 Hz), 6.93-7.70 (m,
70 H, C6H5) ppm. 31P NMR (C6D6): δ 38.0 (s, PPh3, Ru-enynyl),
40.6 (s, PPh3, Ru-alkenylBut) ppm. MS (FAB): m/z (%) 1693 (1)
[M - alkenyl - 2CO]+, 1568 (1) [M - PPh3]+, 1483 (2) [M -
alkenyl - PPh3]+, 1365 (3) [M - PPh3 - enynyl]+, 1303 (4) [M
- 2 PPh3]+. Anal. Found: C, 66.9; H, 4.9; N, 1.4. Calcd for
C102H90N2O2P4Ru2S4: C, 66.9; H, 5.0; N, 1.5.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHC6H4Me-4)(CO)(PPh3)2}] (15). This compound was
prepared as for the synthesis of 14 using [Ru(C(Ct CPh)dCHPh)
(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 100 mg, 0.095 mmol), triethy-
lamine(4drops,excess),CS2(2drops,excess),and[Ru(CHdCHC6H4Me-
4)Cl(BTD)(CO)(PPh3)2] (89 mg, 0.094 mmol) to yield an orange
powder. Yield: 110 mg (62%). IR (CH2Cl2): 2154 (νCt C), 1925
(νCO) cm-1. IR (Nujol): 2148 (νCt C), 1920 (νCO), 1591, 1231, 1001
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHFc)(CO)(PPh3)2}] (19). This compound was prepared as
for
the
synthesis
of
14
using
[Ru(C(Ct CPh)d
CHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 59 mg, 0.056 mmol),
triethylamine (3 drops, excess), CS2 (2 drops, excess), and
[Ru(CHdCHFc)Cl(CO)(PPh3)2] (9; 50 mg, 0.056 mmol) to yield
a yellow-green product. Yield: 80 mg (73%). IR (CH2Cl2): 2151
(νCt C), 1922 (νCO) cm-1. IR (Nujol): 2154 (νCt C), 1917 (νCO), 1589,
1213, 1186, 999 (νC-S) cm-1. 1H NMR (CD2Cl2): δ 2.65-3.18 (m,
8 H, NC4H8N), 3.63, 3.83 (s(br) × 2, 4 H, C5H4), 3.73 (s, 5 H,
Cp), 6.30 (s(br), 1 H, dCHPh), 6.32 (d, 1 H, dCHFc, JHH ) 17.0
Hz), 6.93-7.68 (m, 70 H + 1 H, C6H5 + RuCH) ppm. 31P NMR
(CD2Cl2): δ 37.8 (s, PPh3, Ru-enynyl), 39.3 (s, PPh3, Ru-alkenylFc)
ppm. MS (FAB): m/z (%) 1540 (1) [M - alkenyl - enynyl]+, 1380
(2) [M - 2PPh3 - 2CO]+. Anal. Found: C, 66.2; H, 4.5; N, 1.6.
Calcd for C108H90FeN2O2P4Ru2S4: C, 66.3; H, 4.6; N, 1.4.
1
(νC-S), 917, 847 cm-1. H NMR (CD2Cl2): 2.26 (s, 3 H, CH3),
2.44-3.12 (m, 8 H, NC4H8N), 5.67 (d, 1 H, dCHC6H4Me-4, 3JHH
) 15.3 Hz), 6.27 (s(br), 1 H, dCHPh), 6.76, 6.92 ((AB)2, 4 H,
C6H4, JAB ) 7.7 Hz), 7.02-7.97 (m, 70 H, C6H5), 8.45 (d, 1 H,
3
RuCH, JHH ) 15.2 Hz) ppm. 31P NMR: δ 27.8 ppm (s, PPh3,
Ru-tolyl), 37.6 (s, PPh3, Ru-enynyl). MS (MALDI): m/z (%) 1749
(1) [M - alkenyl]+, 1487 (1) [M - alkenyl - PPh3]+, 1200 (2)
[M - alkenyl - 2PPh3 - CO]+, 1022 (3) [M - alkenyl - enynyl
- 2PPh3]+. Anal. Found: C, 67.3; H, 4.6; N, 1.4. Calcd for
C105H88N2O2P4Ru2S4: C, 67.7; H, 4.8; N, 1.5.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Os-
(CHdCHC6H4Me-4)(CO)(PPh3)2}] (20). This compound was
prepared as for the synthesis of 14 using [Ru(C(Ct -
CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 100 mg, 0.095
mmol), triethylamine (5 drops, excess), CS2 (3 drops, excess), and
[Os(CHdCHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] (98 mg, 0.095 mmol)
to provide an orange product. Yield: 106 mg (57%). IR (CH2Cl2):
2150 (νCt C), 1927 (νCO) cm-1. IR (Nujol): 2149 (νCt C), 1925 (νCO),
1592, 1278, 1215, 999 (νC-S), 910 cm-1. 1H NMR: δ 2.22 (s, 3 H,
CH3), 2.55-2.89 (m, 8 H, NC4H8N), 5.55 (d, 1 H, dCHC6H4Me-
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHCPh2OH)(CO)(PPh3)2}] (16). This compound was pre-
pared as for the synthesis of 14 using [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 80 mg, 0.076
mmol), triethylamine (4 drops, excess), CS2 (2 drops, excess), and
[Ru(CHdCHCPh2OH)Cl(BTD)(CO)(PPh3)2] (78 mg, 0.075 mmol)
to provide an orange-brown powder. Yield: 100 mg (67%). IR
(CH2Cl2): 2152 (νCt C), 1924 (νCO) cm-1. IR (Nujol): 2147, 1922
1
3
(νCO), 1593, 1279, 1231, 1187, 999 (νC-S), 911 cm-1. H NMR
4, JHH ) 15.6 Hz), 6.24 (s(br), 1 H, dCHPh), 6.32, 6.81 ((AB)2,
(d6-acetone): δ 2.40-3.09 (m, 8 H, NC4H8N), 5.12 (d, 1 H,
dCHCPh2OH, 3JHH ) 15.5 Hz), 6.35 (s, 1 H, dCHPh), 7.02-7.69
(m, 80 H, C6H5), 8.03 (m, 1 H, RuCH) ppm. 31P NMR: δ 34.0 (s,
PPh3, Ru-hydroxyalkenyl), 37.5 (s, PPh3, Ru-enynyl) ppm. MS
(FAB): m/z (%) 1951 (1) [M]+, 1521 (2) [M - alkenyl - enynyl
- CO]+. Anal. Found: C, 68.1; H, 4.8; N, 1.5. Calcd for
C111H92N2O3P4Ru2S4: C, 68.2; H, 4.7; N, 1.4.
4 H, C6H4, JAB ) 7.4 Hz), 6.93-7.56 (m, 70 H, C6H5), 8.26 (d, 1
3
H, RuCH, JHH ) 15.6 Hz) ppm. 31P NMR: δ 8.1 (s, OsPPh3),
38.0 (s, RuPPh3) ppm. MS (FAB): m/z (%) 1953 (2) [M]+, 1692
(6) [M - PPh3]+, 1574 (7) [M - PPh3 - alkenyl]+ 1429 (5) [M -
2PPh3]+. Anal. Found: C, 64.3; H, 4.4; N, 1.5. Calcd for
C105H88N2O2OsP4Ru2S4: C, 64.6; H, 4.5; N, 1.4.
[Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)Os-
(CHdCHFc)(CO)(PPh3)2] (21). This compound was prepared
as for the synthesis of 14 using [Ru(C(Ct CPh)d
CHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1) (190 mg, 0.180 mmol),
triethylamine (4 drops, excess), CS2 (3 drops, excess) and
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(CHdCHCO2Me)(CO)(PPh3)2}] (17). This compound was pre-
pared as for the synthesis of 14 using [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 100 mg, 0.095

Bi-, Tri-, and Tetrametallic Complexes of Ru(II) and Os(II)
Organometallics, Vol. 28, No. 1, 2009 207
Table 1. Crystal Data and Structure Refinement Parameters for
[Os(CHdCHFc)Cl(CO)(BTD)(PPh3)2] (10) (200 mg, 0.178 mmol),
stirred for 2 h, to give a black product. Yield: 310 mg (84%). IR
(CH2Cl2): 2152 (νCt C), 2022, 1927 (νCO) cm-1. IR (Nujol): 2149
(νCt C), 1924 (νCO), 1591, 1216, 1188, 1279, 1000 (νC-S) cm-1. 1H
NMR (acetone-d6): δ 3.43-4.00 (m, 8 H, NC4H8N), 4.21 (s, 5 H,
C5H5), 4.57, 4.73 (s(br) × 2, 4 H, C5H4), 6.35 (s, 1 H, dCHPh),
6.46 (d, 1 H, dCHFc, 3JHH ) 15.0 Hz), 6.90-7.70 (m, 70 H, C6H5),
1 · 1.25EtOH
chem formula
fw
C60.5H58.5ClN2O2.25P2RuS2
1112.17
cryst syst
cryst color
cryst size (mm)
space group
a (Å)
monoclinic
yellow
0.22 × 0.17 × 0.02
P21/c
3
8.04 (dt, 1 H, OsCH, JHH ) 15.0 Hz, JHP unresolved) ppm. 31P
21.2542(6)
16.2199(5)
18.9949(6)
90
105.006(2)
90
6325.0(3)
4
1.168
NMR: δ 7.9 (s, OsPPh3), 37.9 (s, RuPPh3) ppm. MS (LSIMS): m/z
(%) 1784 (1) [M - PPh3]+, 1524 (4) [M - 2PPh3]+. Anal. Found:
C, 63.3; H, 4.4; N, 1.4. Calcd for C108H90FeN2O2OsP4RuS4: C, 63.4;
H, 4.4; N, 1.4.
b (Å)
c (Å)
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
[Ru(C(Ct CPh)dCHPh)(CS)(PPh3)2(S2CNC4H8NH2)]Cl (22).
The reagent S2CNC4H8NH2 (13 mg, 0.080 mmol) was dissolved
in methanol (8 cm3), and the complex [Ru(C(Ct
CPh)dCHPh)Cl(CS)(PPh3)2] (50 mg, 0.055 mmol) in dichlo-
romethane (20 cm3) was added. After the mixture was stirred at
room temperature for 1 h, during which a change from orange to
yellow was observed, the volatiles were removed. The crude product
was dissolved in a small amount of dichloromethane, and ethanol
(10 cm3) was added. Slow concentration under reduced pressure
gave a yellow product, which was filtered off, washed with hexane
(10 cm3), and dried under vacuum. Yield: 40 mg (68%). IR
(CH2Cl2): 2145 (νCt C) cm-1. IR (Nujol): 2150 (νCt C), 1246 (νCS),
Z
Dcalcd (g/cm3)
T (K)
150(2)
0.446
2306
µ(Mo KR) (mm-1
F(000)
)
no. of rflns collected
no. of unique rflns/data (Rint)
R1 (I > 2σ(I))
wR2 (I > 2σ(I))
R1 (all data)
40 498
13 562/698 (0.0817)
0.0698
0.1697
0.1196
wR2 (all data)
0.1974
then removed under reduced pressure. The yellow product was taken
up in a small amount of dichloromethane and filtered through
diatomaceous earth. Ethanol (10 cm3) was added,and the solvent
volume was reduced by rotary evaporation. The product was filtered
off, washed with hexane (15 cm3), and dried under vacuum. Yield:
47 mg (55%). IR (CH2Cl2): 2152 (νCt C), 1926 (νCO) cm-1. IR
(Nujol): 2152 (νCt C), 1925 (νCO), 1592, 1278, 1216, 1157, 999
(νC-S), 908 cm-1. 1H NMR: δ 3.08-3.29 (m, 16 H, NC4H8N), 6.30
(s, 2 H, Hꢀ), 6.93-7.55 (m, 80 H, C6H5) ppm. 31P NMR: δ 38.0 (s,
PPh3) ppm. MS (FAB): m/z (%) 1691 (2) [M - 2PPh3 - CO]+.
Anal. Found: C, 63.0; H, 4.3; N, 2.5. Calcd for
C118H98N4O2P4Ru2S8Ni: C, 63.1; H, 4.4; N, 2.5.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2Pd] (26).
This compound was prepared as for the synthesis of 25 using
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 80 mg,
0.076 mmol), triethylamine (4 drops, excess), CS2 (2 drops, excess),
and [PdCl2(NCMe)2] (9.8 mg, 0.038 mmol) to provide a brown
1
999 (νC-S), 893, 846 cm-1. NMR (d6-acetone) H: δ 3.10, 3.31 (s
× 2, 8 H, NC4H8N), 6.42 (s, 1 H, Hꢀ), 6.69-7.45 (m, 40 H, C6H5)
ppm. 31P NMR: 37.0 (s, PPh3) ppm. MS (FAB): m/z (%) 1035 (1)
[M]+. Anal. Found: C, 64.9; H, 4.8; N, 2.7. Calcd for
C58H51N2P2RuS3: C, 65.1; H, 4.8; N, 2.6.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru-
(C(Ct CPh)dCHPh)(CS)(PPh3)2}] (23). This compound was
prepared as for the synthesis of 14 using [Ru(C(Ct
CPh)dCHPh)(S2CNC4H8NH2)(CS)(PPh3)2]Cl (22; 50 mg, 0.047
mmol), triethylamine (1 drop, excess), CS2 (1 drop, excess), and
[Ru(C(Ct CPh)dCHPh)Cl(CO)(PPh3)2] (42 mg, 0.047 mmol) to
give a yellow-brown product. Yield: 67 mg (73%). IR (CH2Cl2):
2153 (νCt C), 1923 (νCO), 1606 cm-1. IR (Nujol): 2150 (νCt C), 1921
1
(νCO), 1592, 1259 (νCS), 1260, 999 (νC-S) cm-1. H NMR (C6D6):
δ 2.08-3.25 (m, 8 H, NC4H8N), 6.35 (s(br), 2 H, Hꢀ), 6.92-7.99
(m, 80 H, C6H5) ppm. 31P NMR: δ 34.1 (s(br), PPh3) ppm. MS
(MALDI): m/z (%) 1702 (2) [M - PPh3]+, 1557 (2) [M -
2(enynyl)]+. Anal. Found: C, 68.3; H, 4.4; N, 1.2. Calcd for
product. Yield: 49 mg (56%). IR (CH2Cl2): 2152 (νCt C), 1927 (νCO
)
cm-1. IR (Nujol): 2152 (νCt C), 1921 (νCO), 1592, 1277, 1217, 1158,
999 (νC-S) cm-1. 1H NMR: δ 2.82-3.40 (m, 16 H, NC4H8N), 6.28
(s, 2 H, Hꢀ), 6.92-7.67 (m, 80 H, C6H5) ppm. 31P NMR: δ 38.0 (s,
PPh3) ppm. MS (FAB): m/z (%) 1859 (1) [M - 2 alkenyl - CO]+,
1199 (1) [M - Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2]+. Anal. Found:
C, 61.8; H, 4.3; N, 2.5. Calcd for C118H98N4O2P4Ru2S8Pd: C, 61.8;
H, 4.3; N, 2.4.
C
112H90N2OP4Ru2S5: C, 68.4; H, 4.6; N, 1.4.
[{Ru(Ct CBut)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (24). [{Ru(CHd
CHC6H4Me-4)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (4; 80 mg, 0.045
mmol) and HCt CBut (28 mg, 0.341 mmol) were heated under
reflux in toluene for 3 h. All solvent was removed under reduced
pressure, the product was taken up in a small amount of dichlo-
romethane, and this mixture was filtered through diatomaceous
earth. Ethanol (15 cm3) was added, and a tan powder was obtained
by reducing the solvent volume. This was filtered off, washed with
hexane (10 cm3), and dried under vacuum. Yield: 54 mg (70%).
IR (CH2Cl2): 2103 (νCt C), 1941 (νCO) cm-1. IR (Nujol): 2102
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2Pt] (27).
This compound was prepared as for the synthesis of 25 using
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 50 mg,
0.047 mmol), triethylamine (3 drops, excess), CS2 (2 drops, excess),
and [PtCl2(NCPh)2] (11.2 mg, 0.024 mmol) to yield a yellow
1
(νCt C), 1947 (νCO), 1279, 1215 cm-1. H NMR (C6D6): δ 0.94 (s,
product. Yield: 32 mg (56%). IR (CH2Cl2): 2153 (νCt C), 1931 (νCO
)
18 H, But), 1.95-2.24 (m, 8 H, NC4H8N), 6.73-7.89 (m, 60 H,
C6H5) ppm. 31P NMR: δ 38.9, 39.3 (s × 2, PPh3) ppm. MS
(MALDI): m/z (%) 1706 (2) [M]+, 1444 (2) [M - PPh3]+, 1418
(4) [M - CO - PPh3]+, 1307 (4) [M - alkynyl - 2CO - PPh3]+.
Anal. Found: C, 61.8; H, 4.7; N, 1.9. Calcd for
C92H86N2O2P4Ru2S4 · 1.5CH2Cl2: C, 61.3; H, 4.9; N, 1.5.
cm-1. IR (Nujol): 2152 (νCt C), 1928 (νCO), 1278, 1217, 1158, 1000
1
(νC-S) cm-1. H NMR: δ 2.78-3.30 (m, 16 H, NC4H8N), 6.30 (s,
2 H, Hꢀ), 6.85-7.72 (m, 80 H, C6H5) ppm. 31P NMR: δ 38.1 (s,
PPh3) ppm. MS (FAB): m/z (%) 2177 (2) [M - enynyl]+, 1981 (1)
[M - 2 enynyl]+, 1687 (1) [M - 2 enynyl - PPh3 - CO]+, 1550
(2) [M - Ru(enynyl)(PPh3)2]+. Anal. Found: C, 59.4; H, 4.3; N,
2.3. Calcd for C118H98N4O2P4PtRu2S8: C, 59.5; H, 4.2; N, 2.4.
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2Zn] (28).
This compound was prepared as for the synthesis of 25 using
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 50 mg,
0.047 mmol), triethylamine (3 drops, excess), CS2 (2 drops, excess),
and [Zn(O2CMe)2] · 2H2O (5.2 mg, 0.024 mmol) to yield a yellow
[{Ru(C(Ct CPh)dCHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2Ni] (25).
[Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)(PPh3)2]Cl (1; 80 mg,
0.076 mmol) was dissolved in dichloromethane (15 cm3) and
methanol (8 cm3). Triethylamine (4 drops, excess) and CS2 (3 drops,
excess) were added. After the mixture was stirred for 5 min,
[Ni(O2CMe)2] (6.7 mg, 0.038 mmol) in dichloromethane (5 cm3)
was added, the mixture was stirred for 2 h, and all solvent was
product. Yield: 55 mg (52%). IR (CH2Cl2): 2152 (νCt C), 1926 (νCO
)

208 Organometallics, Vol. 28, No. 1, 2009
Macgregor et al.
cm-1. IR (Nujol): 2152 (νCt C), 1923 (νCO), 1573, 1277, 1214, 1155,
999 (νC-S) cm-1. 1H NMR: δ 2.62-3.61 (m, 16 H, NC4H8N), 6.25
(s, 2 H, Hꢀ), 6.89-7.51 (m, 80 H, C6H5) ppm. 31P NMR: δ 38.0 (s,
PPh3) ppm. MS (FAB): m/z (%) 1397 (1) [M - Ru(enynyl)-
(CO)(PPh3)2]+. Anal. Found: C, 59.5; H, 3.8; N, 2.4. Calcd for
C118H98N4O2P4Ru2S8Zn · 2CH2Cl2: C, 59.5; H, 4.2; N, 2.3.
positioned geometrically and refined using a riding model. In
addition to the [Ru(C(Ct CPh)dCHPh)(S2CNC4H8NH2)(CO)-
(PPh3)2]+ (1) cation, there are also disordered solvent molecules
and chloride counteranions which were located in the difference
map. The chloride ion was refined using a model where it was split
over three sites with occupancies of 0.65, 0.18, and 0.17 for Cl1,
Cl1A, and Cl1B, respectively. Five partially occupied ethanol
molecules were clearly visible in the difference map and refined
with 25% occupancy each, using the same distance restraint to
maintain plausible geometries. Crystal data and structure refinement
parameters are included in Table 1.
Crystallographic Studies. Crystals of 1 were grown by slow
diffusion of ethanol into a dichloromethane solution of the complex
and subsequent slow evaporation. Single-crystal X-ray diffraction
data were collected using graphite-monochromated Mo KR radiation
(λ ) 0.710 73 Å) on an Enraf-Nonius KappaCCD diffractometer
equipped with a Cryostream N2 open-flow cooling device33 at
150(2) K. Series of ω scans were performed in such a way as to
cover a sphere of data to a maximum resolution of 0.77 Å.
Cell parameters and intensity data for 1 were processed using
the DENZO-SMN package,34 and the structure was solved by direct
methods and refined by full-matrix least squares on F2 using
SHELXTL software.35 Intensities were corrected for absorption
effects by the multiscan method based on multiple scans of identical
and Laue equivalent reflections (using the SORTAV software).36
Where possible, non-hydrogen atoms were refined with aniso-
tropic displacement parameters and the hydrogen atoms were
Crystallographic data (excluding structure factors) for the
structure of 1 have been deposited with the Cambridge Crystal-
lographic Data Centre (CCDC 677008). Copies of the data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgment. J.D.E.T.W.-E. gratefully acknowledges
Merton College for the provision of a Fellowship. We thank
the OUP John Fell Fund for consumables and Johnson
Matthey Ltd for a generous loan of ruthenium and osmium
salts.
(33) Cosier, J.; Glazer, A. M. J. Appl. Crystallogr. 1986, 19, 105.
(34) Otwinowski, Z.; Minor, W. In Processing of X-ray Diffraction Data
Collected in Oscillation Mode; Carter, C. W., Sweet, R. M., Eds.; Academic
Press: New York, 1997; Methods in Enzymology 276.
(35) SHELXTL, version 5.1; Bruker Analytical X-ray Instruments Inc.,
Madison, WI, 1999.
Supporting Information Available: A CIF file giving crystal-
lographic data for the structure of 1. This material is available free
of charge via the Internet at http://pubs.acs.org.
(36) Blessing, R. H. Acta Crystallogr. 1995, A51, 33–38.
OM800686F