Synthesis of (dppe)Pt(μ3-S)2{Ru(N)Me2}2, (dppe)Pt(μ3-S)2{Os(N)(CH2 SiMe3)2}2, and related heterometallic complexes

Article abstract of DOI:10.1021/om010477z

The trimethylsilanethiolate complexes of the platinum triad metals (dppe)M(SSiMe₃)₂ (M = Ni, Pd, Pt) and (COD)Pt(SSiMe₃)₂ were prepared by the reaction of NaSSiMe₃ with (dppe)-MCl₂ or (COD)

Full text of DOI:10.1021/om010477z

4700
Organometallics 2001, 20, 4700-4704
Syn th esis of (d p p e)P t(µ3-S)2{Ru (N)Me2}2,
(d p p e)P t(µ3-S)2{Os(N)(CH2SiMe3)2}2, a n d Rela ted
Heter om eta llic Com p lexes
Patricia A. Shapley,* Hong-Chang Liang, and Nancy C. Dopke
Department of Chemistry, University of Illinois, Urbana, Illinois 61801
Received J une 5, 2001
The trimethylsilanethiolate complexes of the platinum triad metals (dppe)M(SSiMe3)2 (M
) Ni, Pd, Pt) and (COD)Pt(SSiMe3)2 were prepared by the reaction of NaSSiMe3 with (dppe)-
MCl2 or (COD)PtI2. These complexes are water-sensitive. New, sulfido-bridged heterobime-
tallic complexes L2M(µ3-S)2{Ru(N)Me2}2 resulted from the reactions of (dppe)Pt(SSiMe3)2,
(COD)Pt(SSiMe3)2, or (dppe)Pd(SSiMe3)2 with [PPh4][Ru(N)Me2Cl2]. The reaction between
(dppe)Pt(SSiMe3)2 and [Os(N)(CH2SiMe3)2(NCMe)2][BF4] produced (dppe)Pt(µ3-S)2{Os(N)-
(CH2SiMe3)2}2. All new compounds have been characterized through spectroscopic techniques
and elemental analysis. The molecular structures of (dppe)Pt(µ3-S)2{Ru(N)Me2}2 and (dppe)-
Pt(µ3-S)2{Os(N)(CH2SiMe3)2}2 were determined by single-crystal X-ray diffraction.
In tr od u ction
Sulfido ligands are common bridging groups in metal
cluster complexes.7 Many of the rational syntheses of
heteronuclear compounds with bridging sulfido ligands
involve displacing a ligand on a metal center with a
terminal sulfido ligand on another metal.8
Due to the ease in which the Si-S bond can be cleaved
by halides or oxygen nucleophiles, trialkyl- or trialkoxy-
silanethiolate complexes may be viewed as protected
metal sulfides.9,10 The reactivity of silanethiolate com-
plexes of transition metals at both the sulfur and silicon
atoms of the ligand has lead research groups to prepare
alkoxysilanethiolate complexes of cobalt(II) and cobalt-
(III)11 and alkylsilanethiolate complexes of ruthenium-
(II).12 We have previously shown that the reaction
between a trimethylsilanethiolatoruthenium(VI) com-
plex and a chloroosmium(VI) complex produces the
Heterometallic catalysts may have advantages over
monometallic catalysts if the metals act cooperatively
in chemical transformations.1 Many heterometallic com-
plexes have been prepared, including a few that show
catalytic activity.2 Studies of homogeneous Ru-Pt het-
erometallic complexes in particular may improve our
understanding of platinum-containing alloys in catalytic
industrial processes and aid in the development of more
efficient fuel cells.3 The addition of ruthenium to
platinum catalysts greatly improves their activities for
methanol oxidation, and the activity is sensitive to
structure.4 Although a handful of Ru-Pt heterometallic
complexes have been synthesized,5 only CpRu(PPh3)(µ-
Cl)(µ-dppm)PtCl2 has been shown to be an electrocata-
lyst for methanol oxidation.6
There are many strategies for synthesizing hetero-
metallic complexes including bridge-assisted reactions.
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2000, 19, 918-924. (b) Orth, S. D.; Terry, M. R.; Abboud, K. A.; Dodson,
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J . B.; Stacy, A. M.; Spencer, B.; Englert, M. H.; Dahl, L. F. J . Am.
Chem. Soc. 1991, 113, 7396-7410. (c) Mathur, P.; Chakrabarty, D.;
Hossain, M. M.; Rashid, R. S. J . Organomet. Chem. 1991, 420, 79-86.
(d) Adams, R. D.; Pompeo, M. P.; Wu, W. Inorg. Chem. 1991, 30 (14),
2899-2905. (e) Adams, R. D.; Chen, G.; Pompeo, M. P.; Sun, S.
Polyhedron 1990, 9, 3285-3291. (f) Vahrenkamp, H. Inorg. Synth.
1989, 26, 351-356.
(8) (a) Seino, H.; Arai, Y.; Iwata, N.; Nagao, S.; Mizobe, Y.; Hidai,
M. Inorg. Chem. 2001, 40, 1677-1682. (b) Ikada, T.; Kuwata, S.;
Mizobe, Y.; Hidai, M. Inorg. Chem. 1998, 37, 5793-5797. (c) Brunner,
H.; Challet, S.; Kubicki, M. M.; Leblanc, J .-C.; Moise, C.; Volpato, F.;
Wachter, J . Organometallics 1995, 14, 6323-6324. (d) Massa, M. A.;
Rauchfuss, T. B.; Wilson, S. R. Inorg. Chem. 1991, 30, 4667-4669.
(9) (a) Chisholm, M. H.; Cook, C. M.; Huffman, J . C.; Steib, W. E.
Organometallics 1993, 12, 2677-2685. (b) Chisholm, M. H.; Cook, C.
M.; Huffman, J . C.; Martin, J . P. Organometallics 1993, 12, 2354-
2359 (c) Covert, K. J .; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J . Inorg.
Chem. 1992, 31, 66-78. (d) J ernakoff, P.; Cooper, N. J . Organometallics
1986, 5, 747-751.
(1) (a) Stephan, D. W. Coord. Chem. Rev. 1989, 95, 41-107. (b)
Kovacs, J . A.; Bergman, R. G. J . Am. Chem. Soc. 1989, 111, 1131-
1133. (c) Dobbs, D. A.; Bergman, R. G. J . Am. Chem. Soc. 1992, 114,
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S.; Kubicki, M. M.; Leblanc, J .-C.; Moise, C.; Volpato, F.; Wachter, J .
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10.1021/om010477z CCC: $20.00 © 2001 American Chemical Society
Publication on Web 10/04/2001

Synthesis of (dppe)Pt(µ3-S)2{Ru(N)Me2}2
Organometallics, Vol. 20, No. 22, 2001 4701
Sch em e 1
NaSSiMe3 in THF produces (dppe)Pt(SSiMe3)2 (1) in
83% yield. We obtain (COD)Pt(SSiMe3)2 (2) in 48% yield
from the reaction between (COD)PtI2 and NaSSiMe3.
The palladium compound (dppe)Pd(SSiMe3)2 (3) results
from the reaction between (dppe)PdCl2 and NaSSiMe3
in 85% yield. An analogous reaction produces the nickel-
(II) complex (dppe)NiCl2 (4) in 87% yield.
The IR and NMR spectra and the elemental analyses
of all these compounds are consistent with their formu-
1
lation. The H NMR spectra for each compound show a
single peak for the methyl protons of the equivalent
trimethylsilanethiolate groups. The 31P NMR spectra of
1, 3, and 4 each show a resonance for the equivalent
phosphorus atoms of the diphenylphosphinoethane
ligand. There are 31P-195Pt satellites for the peak in
the spectrum of 1.
Sch em e 2
The (trimethylsilyl)methyl complexes are water sensi-
tive. They react with water to generate sulfhydryl
complexes and hexamethyldisiloxane. For example,
(dppe)Ni(SSiMe3)2 reacts with adventitious water in
acetone to form the previously reported sulfhydryl
complex (dppe)Ni(SH)2 in greater than 90% yield by 1H
NMR spectroscopy.15
Sch em e 3
A general route to heterometallic µ-sulfido complexes
employs the reaction of one of the trimethylsilanethi-
olate complexes 1-3 with [PPh4][Ru(N)Me2Cl2]. The
reactions liberate volatile chloro(trimethyl)silane (Scheme
3). The reaction of [PPh4][Ru(N)Me2Cl2] with 1/2 equiv
of (dppe)Pt(SSiMe3)2 or (COD)Pt(SSiMe3)2 produces the
trinuclear heterometallic complexes (dppe)Pt(µ3-S)2{Ru-
(N)Me2}2 or (COD)Pt(µ3-S)2{Ru(N)Me2}2, respectively,
in 72% and 53% yields (Scheme 1). The reaction between
[PPh4][Ru(N)Me2Cl2] and (dppe)Pd(SSiMe3)2 forms
(dppe)Pd(µ3-S)2{Ru(N)Me2}2 in 62% yield. Complexes 5
and 7 are crystalline solids, while 6 is isolated as an
analytically pure oil.
The analogous osmium chloride [N(n-Bu)4][Os(N)-
(CH2SiMe3)2Cl2] does not react with (dppe)Pd(SSiMe3)2
under the same conditions as [PPh4][Ru(N)Me2Cl2]. The
lower reactivity could be due to the greater size of the
(trimethylsilyl)methyl ligands on osmium over the
methyl ligands on ruthenium or to the greater lability
of second-row transition elements over third-row ele-
ments. The reaction between [N(n-Bu)4][Os(N)(CH2-
SiMe3)2Cl2] and 2 equiv of AgBF4 in acetonitrile pro-
duces the more reactive solvate complex [BF4][Os(N)-
(CH2SiMe3)2(NCMe)2]. The trimetallic complex (dppe)-
heterobimetallic species [PPh4][Me3(N)Ru(µ-S)Os(N)(CH2-
SiMe3)2(NCCH3)] and chloro(trimethyl)silane.13 Similar
bridge-building reactions have been employed to pro-
duce a sulfido-bridged Fe(III) octaethylporphyrin dimer.14
Here we report the syntheses of ruthenium(VI) and
osmium(VI)-platinum(II) µ-sulfido complexes and re-
lated heterometallic species from trimethylsilanethi-
olate complexes of the platinum group metals.
Resu lts a n d Discu ssion
Trimethylsilanethiolate complexes of platinum(II) and
palladium(II) are convenient precursors to mixed metal
complexes. The reaction between (dppe)PtCl2 and
Sch em e 4

4702 Organometallics, Vol. 20, No. 22, 2001
Shapley et al.
Ta ble 1. Selected Bon d Dista n ces a n d An gles for 5
a n d 8
5
8
M1-N1, Å [av both N-M] 1.608(8) [1.607] 1.627(5)
[1.637]
M1-S1, Å [av all S- M]
2.425(2) [2.422] 2.4128(16) [2.407]
Pt-S1, Å [av both Pt-S] 2.365(2) [2.368] 2.3574(14) [2.359]
Pt-P1, Å [av both Pt-P] 2.264(2) [2.264] 2.2393(16) [2.244]
M1-Pt, Å [av both M-Pt] 3.1595(7)
3.1968(3) [3.178]
103.9(4) [104.7] 103.6(2) [104.9]
N1-M1-C1, deg
[av N-M-C]
N1-M1-S1, deg
[av N-M-S]
114.3(3) [112.5] 107.96(19) [111.4]
S1-Pt-S2, deg
S1-Pt-P1, deg
80.54(7)
96.58(7)
80.55(5)
97.70(5)
(II) center is square planar. The three metals are
bridged by two sulfido ligands. The nitrido ligands are
in the plane of the three metal atoms, and one of these
points toward the platinum center while the other
nitrido group points away from the platinum. It is
because of this orientation that the two ruthenium
centers in 5 and the two osmium centers in 8 are
inequivalent. The two alkyl groups on each ruthenium
or osmium center are displaced above and below the
plane of the metal atoms.
The dark orange complex 5 crystallizes in the P21/n
space group. The Ru(1)-N(1) distance of 1.608(8) Å in
5 is slightly longer than the Ru-N distances of 1.58(1)
Å in [PPh4][Ru(N)Me4]16 and 1.595(6) Å in [PPh4][Ru-
(N)Me3(SH)].13 This could be due to competition between
sulfido and nitrido ligands for π-bonding to the ruthe-
nium d-orbitals, weakening the Ru-N bond. The Ru-
(1)-C(1) distance of 2.108(9) Å is slightly shorter than
2.14 Å of [PPh4][Ru(N)Me4]. The C(1)-Ru(1)-C(1) angle
is 83.6(4)° in 5, close to that of 83.0° in the tetramethyl
complex. The Pt(1)-P(1) distance of 2.264(2) Å compares
to 2.224(3) Å in (dppe)PtCl2.17 The slightly longer Pt-P
distances in 5 as compared to (dppe)PtCl2 are probably
due to the stronger trans-effect of the sulfido ligands.
The shortest Ru-Pt distance is 3.1977(7) Å, while the
other Ru-Pt distance and the Ru-Ru distance are both
slightly longer than 3.2 Å (Table 1).
Complex 8 crystallizes in the P21/c space group. The
osmium-nitrogen distances in 8 are quite similar to the
Os-N distances in related nitridoosmium(VI) com-
plexes: [N(n-Bu)4][Os3N3(µ3-S)2(CH2SiMe3)6], 1.60(1),
1.61(1), 1.63(1) Å;18 [N(n-Bu)4][Os(N)(CH2SiMe3)2WS4],
1.62(1) Å;19 [Os(N)(CH2SiMe3)2(SNC2H4)]2, 1.62(1) and
1.64(1) Å.20 The trimetallic complex [N(n-Bu)4][Os3N3-
F igu r e 1. Structural diagrams of (dppe)Pt(µ3-S)2{M′(N)-
R2}2.
Pt(µ3-S)2{Os(N)(CH2SiMe3)2}2 forms when solutions of
[BF4][Os(N)(CH2SiMe3)2(NCMe)2] and (dppe)Pd(SSiMe3)2
are combined in air (Scheme 4). We have not analyzed
the silicon-containing byproducts of this reaction, but
because there are no halide ligands lost in this reaction,
it is likely that the S-Si bond of an intermediate
complex is hydrolyzed by adventitious water.
All the complexes (dppe)M(µ3-S)2{Ru(N)Me2}2 are
crystalline solids that are soluble in polar organic
solvents. They are stable to air and water. The 31P NMR
spectra for each complex show a single peak for the
equivalent of phosphorus atoms of the dppe ligand with
Pt-P coupling in the spectra of (dppe)Pt(µ3-S)2{Ru(N)-
Me2}2 and (dppe)Pt(µ3-S)2{Os(N)(CH2SiMe3)2}2. NMR
spectroscopy clearly shows that the ruthenium or os-
mium centers in each of the complexes 5-8 are in-
equivalent. There are two resonances for methyl protons
(10) (a) Wojnowski, W.; Becker, B.; Sassmannshausen, J .; Peters,
E.-M.; Peters, K.; von Schnering, H. G. Zeit. Anorg. Allg. Chem. 1994,
620, 1417-1421. (b) Becker, B.; Wojnowski, W.; Peters, K.; Peters, E.-
M.; von Schnering, H. G. Polyhedron 1992, 11, 613-616. (c) Wojnowski,
W.; Becker, B.; Walz, L.; Peters, K.; Peters, E.-M.; von Schnering, H.
G. Polyhedron 1992, 11, 607-612. (d) Becker, B.; Wojnowski, W.;
Peters, K.; Peters, E.-M.; von Schnering, H. G. Inorg. Chim. Acta 1994,
214, 9-11.
1
in the H NMR spectra of 5-7 and two resonances for
the methyl carbons in the 13C NMR spectra. The 1H
NMR spectrum of 8 shows two resonances for trimeth-
ylsilyl groups and two sets of multiplets for the dia-
sterotopic methylene protons for the equivalent alkyl
groups on two inequivalent osmium centers.
(11) Becker, B.; Zalewska, A.; Konitz, A.; Wojnowski, W. Zeit. Anorg.
Allg. Chem. 2001, 627, 271-279.
(12) Kovacs, I.; Pearson, C.; Shaver, A. J . Organomet. Chem. 2000,
596, 93-203.
(13) Liang, H.-C.; Shapley, P. A. Organometallics 1996, 15, 1331-
1333.
Complexes 5 and 8 were also characterized by single-
crystal X-ray diffraction analyses (Figure 1). Crystals
of 5 used in the X-ray diffraction study were grown from
CH2Cl2 solution and incorporated 1/2 equiv of this
solvent in the lattice. In both cases, the osmium(VI) or
ruthenium(VI) center has a square pyramidal geometry
with an apical terminal nitride ligand. The platinum-
(14) Cai, L.; Holm, R. H. J . Am. Chem. Soc. 1994, 116, 7177-7188.
(15) Schmidt, W.; Hoffmann, G. G.; Holler, R. Inorg. Chim. Acta
1979, 32, L19-L20.
(16) Shapley, P. A.; Kim, H. S.; Wilson, S. R. Organometallics 1988,
7, 928-933.
(17) Engelhardt, L. M.; Patrick, J . M.; Raston, C. L.; Twiss, P.;
White, A. H. Aust. J . Chem. 1984, 37, 2193-2200.
(18) Shapley, P. A.; Liang, H.-C.; Shusta, J . M.; Schwab, J . J .; Zhang,
N.; Wilson, S. R. Organometallics 1994, 13, 3351-3359.

Synthesis of (dppe)Pt(µ3-S)2{Ru(N)Me2}2
Organometallics, Vol. 20, No. 22, 2001 4703
immediately and was stirred for 15 min. The solvent was then
removed under vacuum to yield a yellow residue. The yellow
residue was extracted with hexane and filtered through Celite
to give a yellow solution. The solvent was removed under
vacuum to afford a yellow solid. The solid was used with-
(µ3-S)2(CH2SiMe3)6] is the closest structural analogue
to 8 with similar bond distances and angles for osmium
and the ligating atoms.
Con clu sion
1
out further purification (0.013 g, 0.026 mmol, 48%). H NMR
(400 MHz, CDCl3, 20.5 °C): δ 5.37 (m, 4 H, CH), 2.42 (m, 8 H,
CH2), 0.39 (s, 18 H, PtSSi(CH3)3). 13C{1H} (100 MHz, CDCl3,
20.3 °C): δ 102.9 (t, J Pt-C ) 140 Hz, CH), 30.6 (s, CH2), 6.3 (s,
PtSSi(CH3)3). IR (KBr pellet, cm-1): 2948-2886 (s, νCH), 1414
(m,νCdC), 1238 (s, δSiC), 834 (s, νSiC), 632 (vs), 474 (vs).
P r ep a r a tion of (d p p e)P d (SSiMe3)2, 3. To a magnetically
stirring beige suspension of (dppe)PdCl2 (0.050 g, 0.087 mmol)
in 20 mL of THF was added 2.2 equiv of NaSSiMe3 (0.024 g,
0.19 mmol) all at once. The suspension was stirred for 20 min
until it became a clear, yellow solution. The solvent was then
removed under vacuum to yield a bright yellow solid. The
yellow solid was extracted with ether and filtered through
Celite to yield a yellow solution. The solvent was again
removed under vacuum to yield a bright yellow solid, (dppe)-
Pd(SSiMe3)2 (0.053 g, 0.074 mmol, 85% yield).
We have prepared a series of sulfido-bridged trime-
tallic complexes of the form L2M(µ3-S)2{M′(N)R2}2,
where M is either platinum(II) or palladium(II) and M′
is either ruthenium(VI) or osmium(VI). These complexes
are soluble in a variety of organic solvents and stable
to air and water. We are currently examining the
oxidation of hydrocarbon and alcohol substrates with
these complexes and molecular oxygen.
Exp er im en ta l Section
All reactions were done under nitrogen atmosphere using
standard air-sensitive techniques in a Vacuum Atmospheres
glovebox unless otherwise stated. Anhydrous ether, THF,
toluene, and hexane were distilled from Na/benzophenone.
Methylene chloride and acetonitrile were distilled from CaH2.
Deuterated chloroform was distilled from CaH2 and dried over
molecular sieves. The compounds NaSSiMe3,21 (dppe)NiCl2,22
(dppe)PdCl2,23 (dppe)PtCl2,24 (COD)PtI2,25 [(n-Bu)4N][OsNCl2-
(CH2SiMe3)2],26 and [PPh4][Ru(N)Me2Cl2]16 were synthesized
according to literature procedures. NMR spectra were recorded
on a Varian Unity-400 spectrometer. IR spectra were recorded
on a Perkin-Elmer 1600 series FTIR. Mass spectra were
recorded on a VG ZAB-SE (FAB). All analyses were performed
by the University of Illinois microanalytical service. UV-
visible spectra were recorded on a Hewlett-Packard 8452A
spectrometer.
P r ep a r a tion of (d p p e)Ni(SSiMe3)2, 4. To a magnetically
stirring orange suspension of (dppe)NiCl2 (0.050 g, 0.095 mmol)
in 20 mL of THF was added 2.2 equiv of NaSSiMe3 (0.027 g,
0.21 mmol) all at once. The suspension immediately turned
purple. The purple solution was stirred for 20 min. The solvent
was then removed under vacuum to yield a purple solid. The
purple solid was extracted with ether and filtered through
Celite to yield a clear solution. Excess hexane was added until
the solution became cloudy, and the product crystallized at
-30 °C as dark purple crystals (0.055 g, 0.082 mmol, 87%).
1H NMR (400 MHz, CDCl3, 19.2 °C): δ 7.4-7.8 (m, 20 H,
PC6H5), 2.07 (m, 2 H, PCHaHb), 2.03 (m, 2 H, PCHaHb), 0.024
(s, 18 H, NiSSi(CH3)3). 13C{1H} (100 MHz, CDCl3, 20.3 °C): δ
134.2 (m, p-PC6H5), 130.7 (m, o-PC6H5), 128.4 (m, ipso-PC6H5),
127.5 (m, m-PC6H5), 27.4 (m, PCH2), 6.1 (s, NiSSi(CH3)3). 31P-
{1H} (161.9 MHz, CDCl3, 20.3 °C): δ 48.8 (s). IR (KBr pellet,
cm-1): 3054-2978 (m, νCH), 1483 (s, δCH), 1237 (s, δSiC) 838 (s,
P r ep a r a tion of (d p p e)P t(SSiMe3)2, 1. To a magnetically
stirring suspension of (dppe)PtCl2 (0.050 g, 0.075 mmol) in 20
mL of THF was added 2.2 equiv of NaSSiMe3 (0.021 g, 0.17
mmol) all at once. The suspension was stirred for 20 min, and
it converted to a clear, light yellow solution. The solvent was
removed under vacuum to yield a white solid. The white solid
was extracted with ether and filtered through Celite to yield
a clear solution. Excess hexane was added until the solution
became cloudy. The white product crystallized at -30 °C (0.050
νSiC) Anal. Calcd for NiP2S2Si2C32H42
: C, 57.57; H, 6.34.
Found: C, 57.81; H, 6.21.
Syn th esis of (d p p e)P t(µ3-S)2{Ru (N)Me2}2, 5. A clear
solution of 1 (0.050 g, 0.062 mmol) in 2 mL of CH2Cl2 and an
orange solution of [PPh4][Ru(N)Me2Cl2] (0.069 g, 0.12 mmol)
in 2 mL of CH2Cl2 were both cooled to -30 °C. The solution of
1 was added dropwise to the solution of [PPh4][Ru(N)Me2Cl2],
and the resulting orange solution was immediately placed into
the freezer at -30 °C. After 16 h at -30 °C the solution had
turned red-orange. Hexane was added, and a fluffy, maroon
solid precipitated. The mixture was filtered. The filtercake was
extracted with THF. The THF was then removed from the
maroon solution under vacuum. The resulting solid was
crystallized from CH2Cl2 (0.5 mL) at -30 °C. Dark orange
crystals of 5 (0.042 g, 0.044 mmol, 71%) formed. The crystals
were dried under vacuum. 1H NMR (400 MHz, CDCl3, 20.5
°C): δ 8.0-7.4 (m, 20 H, PC6H5), 2.60-2.16 (m, 4 H, PCH2),
1.75 (s, 6 H, RuaCH3), 1.20 (s, 6 H, RubCH3). 13C{1H} (100 MHz,
CDCl3, 20.3 °C): δ 136.8 (m, p-PC6H5), 132.3 (m, o-PC6H5),
130.2 (m, ipso-PC6H5), 129.3 (m, m-PC6H5), 28.3 (m, PCH2),
5.3 (s, RuaCH3), -0.02 (s, RubCH3). 31P{1H} (161.9 MHz, CDCl3,
20.3 °C): δ 46.01 (t, J Pt-P ) 3159 Hz). IR (KBr pellet, cm-1):
3059-2870 (s, νCH), 1476 (s, δCH) 1069 (vs, νRuN), 756 (vs), 689
(vs), 527 (vs). Anal. Calcd for PtN2P2Ru2S2C30H36: C, 38.01;
H, 3.83; N, 2.96. Found: C, 37.91; H, 3.77; N, 3.15.
1
g, 0.062 mmol, 83%). H NMR (400 MHz, CDCl3, 19.2 °C): δ
7.4-7.8 (m, 20 H, PC6H5), 2.31 (m, 2 H, PCHaHb), 2.27 (m, 2
H, PCHaHb), 0.026 (s, 18 H, PtSSi(CH3)3). 13C{1H} (100 MHz,
CDCl3, 20.3 °C): δ 133.9 (m, p-PC6H5), 131.35 (m, o-PC6H5),
130.4 (m, ipso-PC6H5), 128.5 (m, m-PC6H5), 28.9 (m, PCH2),
6.62 (s, PtSSi(CH3)3). 31P{1H} (161.9 MHz, CDCl3, 20.3 °C):
δ 43.9 (t, J Pt-P ) 2979 Hz). IR (KBr pellet, cm-1): 3054-2978
(m, νCH), 1483 (s, δCH), 1239 (s, δSiC) 836 (s, νSiC) Anal. Calcd
for PtP2S2Si2C32H42: C, 47.80; H, 5.27. Found: C, 47.30; H,
5.47.
P r ep a r a tion of (COD)P t(SSiMe3)2, 2. To a magnetically
stirring yellow solution of (COD)PtI2 (0.030 g, 0.054 mmol) in
20 mL of THF was added 2.2 equiv of NaSSiMe3 (0.015 g, 0.12
mmol) all at once. The yellow solution became lighter yellow
(19) Shapley, P. A.; Gebeyehu, Z.; Zhang, N.; Wilson, S. R. Inorg.
Chem. 1993, 32, 5646-5651.
(20) Zhang, N.; Wilson, S. R.; Shapley, P. A. Organometallics 1988,
7, 1126-1131.
(21) Do, Y.; Simhon, E. D.; Holm, R. H. Inorg. Chem. 1983, 22, 3809-
3812.
(22) Van Hecke, G.; Horrocks, W. D. Inorg. Chem. 1966, 5, 1968-
1974.
Syn th esis of (COD)P t(µ3-S)2{Ru (N)Me2}2, 6. A yellow
solution of 2 (0.013 g, 0.025 mmol) in 2 mL of CH2Cl2 and an
orange solution of [PPh4][Ru(N)Me2Cl2] (0.028 g, 0.050 mmol)
in 2 mL of CH2Cl2 were both cooled to -30 °C. The solution of
2 was then added dropwise to the solution of [PPh4][Ru(N)Me2-
Cl2], and the resulting orange solution was immediately placed
into the freezer at -30 °C. After 16 h at -30 °C the solution
had become yellow. The solvent was removed under vacuum.
(23) J enkins, J . M.; Verkade, J . G. Inorg. Synth. 1968, 11, 108-
111.
(24) Rauchfuss, T. B.; Shu, J . S.; Roundhill, D. M. Inorg. Chem. 1976,
15, 2096-2101.
(25) Clark, H. C.; Manzer, L. E. J . Organomet. Chem. 1973, 59, 411-
428.
(26) Belmonte, P. A.; Own, Z.-Y. J . Am. Chem. Soc. 1984, 106, 7493-
7496.

4704 Organometallics, Vol. 20, No. 22, 2001
Shapley et al.
The yellow residue was extracted with toluene. The toluene
solution was filtered through Celite. The yellow solution was
concentrated under vacuum to yield a yellow solid. The solid
was then washed with CH3CN to remove residual PPh4+ salts
and dried under vacuum (0.009 g, 0.013 mmol, 53%). 1H NMR
(400 MHz, CDCl3, 20.5 °C): δ 5.79-5.41 (m, 4 H, CH), 2.70-
2.29 (m, 8 H, CH2), 1.85 (s, 6 H, RuaCH3), 1.55 (s, 6 H, RubCH3).
13C{1H} (100 MHz, CDCl3, 20.3 °C): δ 97.8 (t, J Pt-C ) 151 Hz,
CaH), 96.12 (t, J Pt-C ) 146 Hz, CbH), 31.2 (s, CcH2), 28.0 (s,
CdH2), 6.9 (s, RuaCH3), 0.4 (s, RubCH3). IR (KBr pellet, cm-1):
2994-2870 (s, δCH), 1456 (s, δCH) 1064 (vs, νRuN), 763 (vs), 692
(vs), 527 (vs). MS (FAB, 3-NBA and magic bullet, neg ion,
m/z): 656.9 (M-, (COD)Pt(µ3-S)2{Ru(N)Me2}2).
1240 (δSiC), 1101 (νOsN), 1061 (δCH), 855 (νSiC), 833 (νSiC). MS
(FD+): (M + H)+ found, 1415.9; calcd, 1416.2. UV-visible
(CH2Cl2, 2.8 × 10-4 M): 258 nm, 298 nm (shd).
Str u ctu r e Deter m in a tion s. The data crystals of 5 were
formed in CH2Cl2 at -30 °C and incorporated 0.5 equiv of
solvent in the crystal lattice. They were mounted using oil
(Paratone-N, Exxon) to a thin glass fiber. Systematic condi-
tions suggested the unambiguous space group P21/n. Scatter-
ing factors and anomalous dispersion terms were taken from
standard tables.27 The structure was solved by direct meth-
ods.28 Non-hydrogen atoms were refined with anisotropic
displacement parameters. Successful convergence of the full-
matrix least-squares refinement on F2 was indicated by the
maximum shift/error for the last cycle.29 The highest peaks in
the final difference map were in the vicinity of the Pt atom. A
final analysis of variance between observed and calculated
structure factors showed no variance on amplitude or resolu-
tion.
Syn th esis of (d p p e)P d (µ3-S)2{Ru (N)Me2}2, 7. A yellow
solution of 3 (0.053 g, 0.074 mmol) in 2 mL of CH2Cl2 was
cooled to -30 °C and added dropwise to a solution of
[PPh4][Ru(N)Me2Cl2] (0.082 g, 0.15 mmol) in 2 mL of CH2Cl2.
The resulting orange solution was immediately placed into the
freezer at -30 °C. After 16 h at -30 °C the solution had
become red-orange. Hexane was added until a fluffy, orange
solid precipitated. The mixture was filtered. The solid was
extracted with THF. Solvent was removed under vacuum from
the dark red THF solution. The resulting dark red solid was
dissolved in a minimal amount of CH2Cl2 (0.5 mL) and stored
at -30 °C. Maroon crystals of 7 formed within 1 day (0.039 g,
0.046 mmol, 62%). 1H NMR (400 MHz, CDCl3, 20.5 °C): δ 7.7-
7.3 (m, 20 H, PC6H5), 2.63-2.24 (m, 4 H, PCH2), 1.70 (s, 6 H,
RuaCH3), 1.19 (s, 6 H, RubCH3). 13C{1H} (100 MHz, CDCl3, 20.3
°C): δ 136.8 (m, p-PC6H5), 132.3 (m, o-PC6H5), 130.2 (m, ipso-
PC6H5), 129.3 (m, m-PC6H5), 26.2 (m, PCH2), 11.9 (s, RuaCH3),
5.3 (s, RubCH3). 31P{1H} (161.9 MHz, CDCl3, 20.3 °C): δ 61.6
The crystals of 8 were grown by slow evaporation of
d-chloroform. The data crystal was mounted using oil (Para-
tone-N, Exxon) to a thin glass fiber with (0 -1 0) scattering
planes roughly normal to the spindle axis. The space group
P2(1)/c (No. 14) was selected on the basis of systematic
conditions and was confirmed by successful convergence of the
full-matrix least-squares refinement on F2.
Ack n ow led gm en t. We gratefully acknowledge the
financial support of the National Science Foundation
(CHE 95-26350) and the donors of the Petroleum
Research Fund, administered by the American Chemi-
cal Society, for support of this work. NMR spectra were
obtained in the Varian Oxford Instrument Center for
Excellence in NMR Laboratory. Funding for this instru-
mentation was provided in part from the W. M. Keck
Foundation, the National Institutes of Health (PHS 1
S10 RR10444-01), and the National Science Foundation
(NSF CHE 96-10502). Purchase of the Siemens Platform/
CCD diffractometer by the School of Chemical Sciences
was supported by National Science Foundation grant
CHE 9503145. We thank Scott R. Wilson and Theresa
Prussak-Wieckowska for collection of crystal data and
helpful discussions in the solving of the crystal struc-
tures.
(s). IR (KBr pellet, cm-1): 3052-2893 (s, νCH), 1481 (s, δCH
)
1066 (vs, νRuN), 750 (vs), 689 (vs), 527 (vs). MS (FAB, 3-NBA
and magic bullet, neg ion, m/z): 857.8 (M-, (dppe)Pd(µ3-S)2-
{Ru(N)Me2}2).
Syn th esis of (d p p e)P t(µ3-S)2[Os(N)(CH2SiMe3)2], 8. A
solution of AgBF4 (0.037 g, 0.19 mmol) in acetonitrile (10 mL)
was added dropwise to an orange solution of [N(n-Bu)4]-
[OsNCl2(CH2SiMe3)2] (0.062 g, 0.09 mmol) in acetonitrile (10
mL). The solution quickly became cloudy and turned yellow.
The volatiles were removed via vacuum, and the product was
extracted with diethyl ether. The volatiles were removed, and
the product was stored in the freezer for use the following day.
A solution of (dppe)Pt(SSiMe3)2 (0.035 g, 0.044 mmol) in
methylene chloride (6 mL) was added dropwise to a solution
of the [Os(N)(CH2SiMe3)2(NCCH3)2][BF4] in methylene chloride
(10 mL). The solution turned orange and was allowed to stir
for 17.5 h. The volatiles were removed via vacuum. The residue
was dissolved in methylene chloride and hexane. A film
precipitated, and an orange solution was decanted. Removal
of the volatiles from the orange solution via vacuum yields a
orange-brown residue that was crystallized from a methylene
Su p p or tin g In for m a tion Ava ila ble: For 5 and 8 tables
of additional crystal data collection and refinement param-
eters, atomic coordinates, distances and angles, and anisotro-
pic displacement parameters. Interested readers are able to
obtain this material free of charge via the Internet at http://
pubs.acs.org.
OM010477Z
1
chloride solution. H NMR (400 MHz, CDCl3): δ 7.9-7.1 (m,
(27) International Tables for X-ray Crystallography; Wilson, A. J .
C., Ed.; Kluwer Academic Publishers: Dordrecht, 1992; Vol. C, (a)
scattering factors, pp 500-502; (b) anomalous dispersion corrections,
pp 219-222.
(28) Sheldrick, G. M. SHELXS-86. Acta Crystallogr. 1990, A46, 467-
473.
(29) Sheldrick, G. M. SHELXL-93, Program for crystal structure
refinement; Institute fur Anorganic Chemie: Gottingen, Germany,
1993.
20H, PC6H5); 2.6-2.4 (m, 4H, PCH2); 2.27 (d, 2H, J ) 10.8
Hz, OsCHaHb); 2.16 (d, 2H, J ) 10.8 Hz, OsCHaHb); 1.74 (d,
2H, J ) 10 Hz, OsCHaHb); 1.45 (d, 2H, J ) 10 Hz, OsCHaHb);
0.059 (s, 18H, SiCH3); -0.070 (s, 18H, SiCH3). 31P{1H} (161.9
1
MHz, CDCl3): δ 46.18 (t, J Pt-P ) 3162 Hz). IR (methylene
chloride solution, cm-1): 3075-3000 (νCH), 2950 (νCH), 2893
(νCH), 2855 (νCH), 1485 (δCH), 1437 (δCH), 1408 (δCH), 1382 (δCH),