Five-coordinate complexes MHCl(CO)(PiPr3)2 (M = Os, Ru) as precursors for the preparation of new hydrido-and alkenyl-metallothiol and monothio-β-diketonato derivatives

Article abstract of DOI:10.1021/om970633v

The five-coordinate complexes MHCl(CO)(PⁱPr₃)₂ (M = Os (1), Ru (2)) react with NaSH to give the unsaturated hydrido-metallothiol derivatives MH(SH)(CO)(PⁱPr₃)₂ (M = Os (3), Ru (4)). Complexes 3 and 4 react with CO to afford the cis-dicarbonyl compounds MH(SH)-(CO)₂(PⁱPr₃)₂ (M = Os (5), Ru (6)). Similarly, the reaction of 3 with P(OMe)₃ leads to OsH-(SH)(CO){P(OMe)₃}(PⁱPr₃)₂ (7). Treatment of 3 with 1 equiv of acetylenedicarboxylic methyl ester affords OsH{SC(CO₂CH₃)CHC(OCH₃)O}(CO)(P ⁱPr₃)₂ (8), which is the result of the trans addition of the S-H bond of 3 to the carbon-carbon triple bond of the alkyne. The structure of 8 was determined by X-ray investigation. The geometry of the complex can be rationalized as a distorted octahedron with the two phosphorus atoms of the triisopropylphosphine ligands occupying apical positions. The equatorial plane is formed by the bidentate ligand, which acts with a bite angle of 89.49(12)°, the hydrido ligand trans-disposed to the oxygen atom, and the carbonyl group trans-disposed to the sulfur atom. Acetylenedicarboxylic methyl ester also reacts with 4 by insertion of the carbon-carbon triple bond into the S-H bond. However, in the resulting monothio-β-diketonato derivative RuH{SC(CO₂CH₃)CHC-(OCH₃)O}(CO)(P ⁱPr₃)₂ (9) the hydrido ligand lies trans to the sulfur atom. In solution, complex 9 isomerizes into 10, containing the hydrido ligand trans-disposed to the oxygen atom of the chelate group. The stereochemistry of 10 was corroborated by X-ray investigation. The geometry of 10 is the same as that of 8, and the structural parameters of both molecules are statistically identical. Phenylacetylene and methylpropiolate, in contrast to acetylene-dicarboxylic methyl ester, react with 3 and 4 by insertion of the carbon-carbon triple bonds into the M-H bonds to give the unsaturated alkenyl-metallothiol complexes M{(CE)-CH=CHPh}(SH)(CO)(PⁱPr₃)₂ (M = Os (11), Ru (12)) and Ru{(CE)-CH=CHCO₂CH₃}(SH)(CO)(Pⁱ-Pr ₃)₂ (13).

Full text of DOI:10.1021/om970633v

5748
Organometallics 1997, 16, 5748-5755
F ive-Coor d in a te Com p lexes MHCl(CO)(P iP r 3)2 (M ) Os,
Ru ) a s P r ecu r sor s for th e P r ep a r a tion of New Hyd r id o-
a n d Alk en yl-Meta lloth iol a n d Mon oth io-â-Dik eton a to
Der iva tives
Mar´ıa L. Buil, Sergio Elipe, Miguel A. Esteruelas,* Enrique On˜ate,
Elena Peinado, and Natividad Ruiz
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-Consejo Superior de Investigaciones Cient´ıficas,
50009 Zaragoza, Spain
Received J uly 24, 1997X
The five-coordinate complexes MHCl(CO)(PiPr3)2 (M ) Os (1), Ru (2)) react with NaSH to
give the unsaturated hydrido-metallothiol derivatives MH(SH)(CO)(PiPr3)2 (M ) Os (3),
Ru (4)). Complexes 3 and 4 react with CO to afford the cis-dicarbonyl compounds MH(SH)-
(CO)2(PiPr3)2 (M ) Os (5), Ru (6)). Similarly, the reaction of 3 with P(OMe)3 leads to OsH-
(SH)(CO){P(OMe)3}(PiPr3)2 (7). Treatment of 3 with 1 equiv of acetylenedicarboxylic methyl
ester affords OsH{SC(CO2CH3)CHC(OCH3)O}(CO)(PiPr3)2 (8), which is the result of the trans
addition of the S-H bond of 3 to the carbon-carbon triple bond of the alkyne. The structure
of 8 was determined by X-ray investigation. The geometry of the complex can be rationalized
as a distorted octahedron with the two phosphorus atoms of the triisopropylphosphine ligands
occupying apical positions. The equatorial plane is formed by the bidentate ligand, which
acts with a bite angle of 89.49(12)°, the hydrido ligand trans-disposed to the oxygen atom,
and the carbonyl group trans-disposed to the sulfur atom. Acetylenedicarboxylic methyl
ester also reacts with 4 by insertion of the carbon-carbon triple bond into the S-H bond.
However, in the resulting monothio-â-diketonato derivative RuH{SC(CO2CH3)CHC-
(OCH3)O}(CO)(PiPr3)2 (9) the hydrido ligand lies trans to the sulfur atom. In solution,
complex 9 isomerizes into 10, containing the hydrido ligand trans-disposed to the oxygen
atom of the chelate group. The stereochemistry of 10 was corroborated by X-ray investigation.
The geometry of 10 is the same as that of 8, and the structural parameters of both molecules
are statistically identical. Phenylacetylene and methylpropiolate, in contrast to acetylene-
dicarboxylic methyl ester, react with 3 and 4 by insertion of the carbon-carbon triple bonds
into the M-H bonds to give the unsaturated alkenyl-metallothiol complexes M{(E)-
CHdCHPh}(SH)(CO)(PiPr3)2 (M ) Os (11), Ru (12)) and Ru{(E)-CHdCHCO2CH3}(SH)(CO)(Pi-
Pr3)2 (13).
In tr od u ction
bene,14 vinylidene,15 π-butadiene,16 acyl,17 aryl,18 and
cyclopentadienyl19 derivatives.
Metallothiols, the inorganic counterpart of the organic
mercaptans, are a class of compounds characterized by
the presence of the M-SH functional group,1,2 which
are presently attracting considerable interest not only
because they are structurally related to metal sulfide
hydrodesulfurization catalysts3 but also because they
provide model compounds for biological systems4 in-
volved inter alia in nitrogen fixation and hydrogenation
processes.
We now prove that the complexes MHCl(CO)(PiPr3)2
(M ) Os, Ru) are also useful starting materials to
prepare new metallothiol complexes. This paper de-
scribes the synthesis and characterization of new five-
and six-coordinate hydrido- and alkenyl-metallothiol
compounds and the unprecedented insertion of acetyl-
enedicarboxylic methyl ester into the S-H bond of the
complexes MH(SH)(CO)(PiPr3)2 (M ) Os, Ru).
Previously, we have reported the synthesis of the five-
coordinate compounds MHCl(CO)(PiPr3)2 (M ) Os, Ru),5
which are active and highly selective catalysts for the
reduction of unsaturated organic substrates6 and for the
addition of HSiEt3 to phenylacetylene.7 These com-
pounds have also been the master key for the develop-
ment of an extensive organometallic chemistry including
mono- and binuclear tetrahydridoborate,8 dihydrogen,9
polyhydrido,10 alkynyl,11 alkenyl,12 acetatovinyl,13 car-
Resu lts a n d Discu ssion
1. Syn th esis a n d Ch a r a cter iza tion of F ive- a n d
Six-Coor d in a te Hyd r id o-Meta lloth iol Com p lexes.
Treatment at room temperature of tetrahydrofuran
solutions of the chloro-hydrido complexes MHCl(CO)-
(PiPr3)2 (M ) Os (1), Ru (2)) with NaSH gives, after
solvent removal, sticky residues. Toluene extraction of
the residues and filtration to remove NaCl afford
solutions from which the five-coordinate hydrido-met-
allothiol complexes MH(SH)(CO)(PiPr3)2 (M ) Os (3),
X Abstract published in Advance ACS Abstracts, November 15, 1997.
S0276-7333(97)00633-X CCC: $14.00 © 1997 American Chemical Society

Five-Coordinate Complexes MHCl(CO)(PiPr3)2
Organometallics, Vol. 16, No. 26, 1997 5749
Sch em e 1
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Hz and 14.8 (3) and 18.0 (4) Hz, respectively. Although
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(3) and 66% (4) yield. Complexes 3 and 4 are very air-
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5750 Organometallics, Vol. 16, No. 26, 1997
Buil et al.
ligand,20 the multiplicity of the -SH resonances sug-
gests that they are monomeric in solution. Further-
more, the chemical shifts of the hydrido ligands and the
stretching frequencies of the carbonyl groups in the IR
spectra in Nujol (1884 (3) and 1900 (4) cm-1) agree well
with those previously reported for the starting com-
plexes 1 (-31.92 ppm and 1886 cm-1 in benzene
solution) and 2 (-24.20 ppm and 1910 cm-1 in benzene
solution) for which square-pyramidal arrangements of
ligands around of the metallic centers have also been
proposed. The T-shape disposition of the hydrido,
carbonyl, and π-donor ligand (SH) with the carbonyl
group trans-disposed to the -SH ligand seems to be the
result of an electronic push-pull mechanism between
the donor and the acceptor ligands.21 The 31P{1H} NMR
spectra show singlets at 44.6 (3) and 61.0 (4) ppm.
We note that the five-coordinate hydrido-metallothiol
complex RuH(SH)(PPh3)3 has been previously prepared
by reaction of RuH2(PPh3)4 with H2S.1m
Six-coordinate hydrido-metallothiol complexes can be
prepared by reaction of 3 and 4 with non bulky Lewis
bases such as CO and P(OMe)3 (Scheme 1). Under
carbon monoxide atmosphere, the diethyl ether solu-
tions of 3 and the pentane solutions of 4 afford the cis-
dicarbonyl derivatives OsH(SH)(CO)2(PiPr3)2 (5) and
RuH(SH)(CO)2(PiPr3)2 (6), respectively. These com-
pounds were isolated as white solids in 89% (5) and 41%
(6) yield. Similar to the reactions of 3 and 4 with carbon
monoxide, complex 3 adds trimethyl phosphite to give
OsH(SH)(CO){P(OMe)3}(PiPr3)2 (7), which was also
isolated as a white solid in 78% yield.
(J H-P′ ) 18.6 Hz) of doublets (J H-H ) 5.1 Hz), as a result
from the coupling with the hydrido ligand and the
phosphorus of the phosphite. Coupling with the phos-
phorus of the triisopropylphosphine is not observed.
For saturated hydrocarbons, the values of the vicinal
3J coupling constants are dependent on the dihedral
angle between the coupled nuclei, according to the
Karplus curves. Thus, the coupling constants are
largest for Φ ) 0° or 180°, and smallest for Φ ) 90°.22
The extrapolation of the Karplus relationship into our
hydrido-metallothiol compounds permits us to make
some interesting conclusions about the disposition of
-SH group in 3-7.
As previously mentioned, the -SH proton of 3 and 4
shows nuclear spin coupling with the phosphorus nuclei
(about 18 Hz) while coupling with the hydrido ligand is
not observed. This suggests that the S-H direction
should be perpendicular to the M-H direction with the
S-H bond pseudo-parallel to P-M-P direction. Fur-
thermore, the equivalence observed in the 31P{1H} NMR
spectra for the phosphine ligands suggests that a fast
change in the orientation of the -SH group ocurrs.
In contrast to 3 and 4, the -SH proton of 5-7 shows
nuclear spin coupling with the hydrido ligand (about 5
Hz) while the values of H-P (P ) PiPr3) coupling
constants are zero (7) or significantly smaller than those
found for 3 and 4 (about 1.5 versus 18 Hz). Further-
more, the value of the H-P′ (P′ ) P(OMe)3) coupling
constant found in 7 (18.6 Hz) is similar to the values of
H-P (P ) PiPr3) coupling constants in 3 and 4. These
data seem to indicate that, in contrast to 3 and 4, the
S-H bond of 5-7 is not parallel to the PiPr3-M-PiPr3
direction but perpendicular.
The cis-relative position of the carbonyl ligands in 5
and 6 was inferred from the IR spectra, which show two
strong ν(CO) bands at 1972 and 1907 cm-1 (5), and 1955
and 1910 (6) cm-1. The -SH resonances appear in the
2. In ser tion of CH3O2C-CtC-CO2CH3 in to th e
S-H Bon d of 3 a n d 4. The addition of a stoichiometric
amount of acetylenedicarboxylic methyl ester to a tet-
rahydrofuran solution of 3 leads to the monothio-â-
1
high-field region of the H NMR spectra, at -2.46 (5)
and -2.96 (6) ppm, in agreement with those previously
reported for other six-coordinate hydrochalcogenide
complexes.1v In contrast to 3 and 4, the -SH hydrogen
atom of 5 and 6 shows nuclear spin coupling with the
corresponding hydrido ligands. Thus, the -SH reso-
nances are observed as doublets of triplets with H-H
and H-P coupling constants of 6.0 (5) and 4.5 (6) Hz
and 1.2 (5) and 1.5 (6) Hz, respectively. The resonances
of the hydrido ligands appear at -6.65 (5) and -6.14
(6) ppm as double triplets with H-P coupling constants
of 21.0 (5) and 20.7 (6) Hz. The 31P{1H} NMR spectra
show singlets at 22.2 (5) and 57.8 (6) ppm.
diketonato complex OsH{SC(CO2CH3)CHC(OCH3)O}-
(CO)(PiPr3)2 (8, in Scheme 2), which is a result of the
unprecedented insertion of the carbon-carbon triple
bond of the alkyne into the S-H bond of 3. Complex 8
was isolated as red crystals in 86% yield.
Figure 1 shows a representation of the molecule of 8.
Selected bond distances and angles are listed in Table
1. Although the hydrido ligand could not be located,
the presence of this ligand in the complex is supported
by the IR and 1H and 31P{1H} NMR spectra. The IR
spectrum in Nujol shows a ν(Os-H) absorption at 2177
cm-1, while the 1H NMR spectrum in benzene-d6
contains a triplet with a H-P coupling constant of 16.2
Hz at -20.26 ppm. The 31P{1H} NMR spectrum shows
a singlet at 22.7 ppm, which is split into a doublet,
under off-resonance conditions, as a result from the
coupling with the hydrido ligand.
The coordination geometry around the osmium atom
could be rationalized as a distorted octahedron with the
two phosphorus atoms of the phosphine ligands occupy-
ing the apical positions (P(1)-Os-P(2) ) 171.17(5)°).
The equatorial plane is formed by the bidentate ligand,
which acts with a bite angle O(2)-Os-S of 89.49(12)°,
the hydrido ligand trans-disposed to O(2) and the
carbonyl group trans-disposed to the sulfur atom (C(1)-
Os-S ) 170.9(2)°).
The spectroscopic data obtained for 7 support the
octahedral structure proposed in Scheme 1. The 31P-
{1H} NMR spectrum consists of a triplet at 102.2 ppm
and a doublet at 13.5 ppm (J P-P ) 18 Hz), in agreement
with a phosphite ligand cis to two equivalent triisopro-
pylphosphine ligands. The proposed trans disposition
of the hydrido and phosphite ligands is supported by
1
the H NMR spectrum, which contains a doublet (J H-P′
) 137.1 Hz) of triplets (J H-P ) 25.6 Hz) of doublets
(J H-H ) 5.1 Hz) at -8.39 ppm. As for 5 and 6, the
high-field region of this spectrum also exhibits the -SH
resonance, which is observed at -2.40 ppm as a doublet
(21) (a) Poulton, J . T.; Folting, K.; Streib, W. E.; Caulton, K. G. Inorg.
Chem. 1992, 31, 3190. (b) Poulton, J . T.; Sigalas, M. P.; Eisenstein,
O.; Caulton, K. G. Inorg. Chem. 1993, 32, 5490. (c) Heyn, R. H.;
Huffman, J . C.; Caulton, K. G. New J . Chem. 1993, 17, 797. (d) Poulton,
J . T.; Sigalas, M. P.; Folting, K.; Streib, W. E.; Eisenstein, O.; Caulton,
K. G. Inorg. Chem. 1994, 33, 1476.
(22) Friebolin, H. Basic One- and Two-Dimensional NMR Spectros-
copy; VCH Verlagsgesell-schaft: Weinheim, 1991, Section 3.2.2.1.

Five-Coordinate Complexes MHCl(CO)(PiPr3)2
Organometallics, Vol. 16, No. 26, 1997 5751
toluene at room temperature, complex 9 is unstable and
evolves into the isomer 10 after 15 min. This compound
similar to 8, contains the hydrido ligand trans-disposed
to the oxygen atom of the chelate group (Scheme 2).
The most significant differences between the spectro-
scopic data of 9 and 10 are the values of the stretching
frequency of the Ru-H bonds in the IR spectra and the
1
chemical shifts of the hydrido ligands in the H NMR
spectra. The ν(Ru-H) band of 9 appears at 2025 cm-1
,
while that of 10 is shifted by 55 cm-1 to higher
wavenumbers (2080 cm-1). The resonance of the hy-
drido ligand of 9 is observed at -9.16 (t, J H-P ) 19.5
Hz) ppm, while the resonance of the hydrido ligand of
10 appears at -17.88 (t, J H-P ) 20.1 Hz) ppm, thus
shifted by 8.72 ppm to higher field. This difference in
chemical shift is similar to that observed (8.78 ppm)
between the chemical shifts of the complexes OsH(κ2-
S2CH)(CO)(PiPr3)2 (-12.80 ppm)9c and OsH(κ2-O2CH)-
(CO)(PiPr3)2 (-21.58 ppm).24 The 31P{1H} NMR spectra
of both isomers show singlets at 54.0 (9) and 47.5 (10)
ppm, which are split into doublets under off-resonance
conditions.
F igu r e 1. Molecular diagram of complex OsH{SC(CO2-
CH3)CHC(OCH3)O}(CO)(PiPr3)2 (8).
The definitive characterization of the stereochemistry
of 10 was obtained from a X-ray diffraction experiment
on a single crystal of the complex. In this case, the
hydrido ligand was located in the difference Fourier
maps and refined as an isotropic atom together with the
rest of the non-hydrogen atoms of the structure, giving
a Ru-H(01) distance of 1.55(3) Å. Figure 2 shows a
representation of the molecule. Selected bond distances
and angles are listed in Table 1. The coordination
geometry around the metallic center is the same as that
of 8. Furthermore, the structural parameters of both
molecules are statistically identical.
The bidentate ligand forms a six-membered, almost
planar ring with the osmium atom. The deviations from
the best plane are -0.000(1) (Os), 0.003(2) (S), 0.014(5)
(O(2)), 0.019(7) (C(20)), -0.039(8) (C(22)), and -0.024-
(8) (C(23)) Å. The observed interatomic distances in the
sequence O(2)-C(20)-C(22)-C(23)-S (1.232(8), 1.428-
(10), 1.371(10), and 1.703(7) Å) agree well with those
found in other monothio-â-diketonato complexes.23 In
‚‚‚
this context, is interesting to note that the C C bond
‚‚‚ ‚‚‚
adjacent to C S is slightly shorter than C C next to
‚‚‚ ‚‚‚
C
S. It follows that C O has more double bond
‚‚‚
character than C S. This indicates that resonance
structure A makes a greater contribution to the elec-
tronic structure than B. The preference for tautomer
Although transition-metal monothio-â-diketonato com-
plexes are known and the addition of methyl acrylate
at the S-H bonds of the complex (η5-C5H5)Ti(µ-SH)2-
Mo(CO)4 has been previously reported,20e it should be
noted that the preparation of this type of compound by
insertion of an internal alkyne into the S-H bond of a
metallothiol complex has no precedent. Recently, we
have also observed that the five-coordinate hydrido-
hydroxo complex OsH(OH)(CO)(PiPr3)2 reacts with acet-
ylenedicarboxylic methyl ester, similarly to 3 and 4, to
A can be rationalized as hydrido preferring the weaker
ligand trans to itself.
Acetylenedicarboxylic methyl ester also reacts with
the ruthenium hydrido-metallothiol complex 4 by
insertion of the carbon-carbon triple bond into the S-H
bond. However, in the resulting monothio-â-diketonato
afford the â-diketonato derivative OsH{OC(OCH3)CHC-
(CO2CH3)O}(CO)(PiPr3)2.25 In contrast to this unsatur-
ated osmium compound, the reaction of the saturated
hydroxo complex Ir(η5-C5Me5)(Ph)(OH)(PMe3) with acet-
ylenedicarboxylic methyl ester leads to Ir(η5-C5Me5)-
(Ph){(Z)-C(CO2CH3)dC(CO2CH3)OH}(PMe3), as result
of the cis-addition of the Ir-O bond to the carbon-
carbon triple bond of the alkyne.26 Similarly, the
reactions of the complexes trans-Pd(C6H4CHdNPh)-
(NHPh)(PMe3)2 and trans-Pd(C6H5)(NHPh) (PMe3)2 with
acetylenedicarboxylic methyl ester result in the cis-
complex RuH{SC(CO2CH3)CHC(OCH3)O}(CO)(PiPr3)2
(9), the hydrido ligand lies trans to the sulfur atom. In
(23) (a) Lippard, S. J .; Morehouse, S. M. J . Am. Chem. Soc. 1969,
91, 2504. (b) Siiman, O.; Titus, D. T.; Cowman, C. D.; Fresco, J .; Gray,
H. B. J . Am. Chem. Soc. 1974, 96, 2353. (c) Casellato, U.; Vigato, P.
A.; Graziani, R.; Vidali, M.; Acone, B. Inorg. Chim. Acta 1980, 45, L79.
(d) Silver, M. E.; Chun, H. K.; Fay, R. C. Inorg. Chem. 1982, 21, 3765.
(e) Depmeier, W.; Dietrich, K.; Ko¨nig, K.; Musso, H.; Weiss, W. J .
Organomet. Chem. 1986, 314, C1. (f) Bandoli, G.; Mazzi, U.; Spies, H.;
Mu¨nze, R.; Ludwig, E.; Ulhemann, E.; Scheller, D. Inorg. Chim. Acta
1987, 132, 177. (g) Botha, L. J .; Basson, S. S.; Leipoldt, J . G. Inorg.
Chim. Acta 1987, 126, 25. (h) Dietrich, K.; Ko¨nig, K.; Mattern, G.;
Musso, H. Chem. Ber. 1988, 121, 1277. (i) Kamenar, B.; Korpar-Cˇ olig,
B.; Cindric´, M.; Penavic´, M.; Strukan, N. J . Chem. Soc., Dalton Trans.
1992, 2093. (j) Cavell, K. J .; J in, H.; Skelton, B. W.; White, A. H. J .
Chem. Soc., Dalton Trans. 1992, 2923. (k) Cavell, K. J .; J in, H.; Skelton,
B. W.; White, A. H. J . Chem. Soc., Dalton Trans. 1993, 1973.
(24) (a) Werner, H.; Tena, M. A.; Mahr, N.; Peters, K.; von Schnering,
H. G. Chem. Ber. 1995, 128, 41. (b) Albe´niz, M. J .; Esteruelas, M. A.;
Lledo´s, A.; Maseras, F.; On˜ate, E.; Oro, L. A.; Sola, E.; Zeier, B. J .
Chem. Soc., Dalton Trans. 1997, 181.
(25) Edwards, A. J .; Elipe, S.; Esteruelas, M. A.; Lahoz, F. J .; Oro,
L. A.; Valero, C. Organometallics 1997, 16, 3828.
(26) Woerpel, K. A.; Bergman, R. G. J . Am. Chem. Soc. 1993, 115,
7888.
(27) Villanueva, L. A.; Abboud, K. A.; Boncella, J . M. Organome-
tallics 1992, 11, 2963.

5752 Organometallics, Vol. 16, No. 26, 1997
Buil et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles (d eg) for th e Com p lexes
OsH{SC(CO2CH3)CHC(OCH3)O}(CO)(P iP r 3)2 (8) a n d Ru H{SC(CO2CH3)CHC(OCH3)O}(CO)(P iP r 3)2 (10)a
Os
Ru
Os
Ru
M-P(1)
M-P(2)
M-H(01)
M-C(1)
M-O(2)
M-S
2.385(2)
2.383(2)
2.3894(6)
2.3871(6)
1.55(3)
1.823(2)
2.2275(14)
2.4319(6)
1.165(3)
O(2)-C(20)
C(20)-C(22)
C(20)-O(3)
C(22)-C(23)
C(23)-C(24)
C(23)-S
1.232(8)
1.428(10)
1.346(8)
1.371(10)
1.511(10)
1.703(7)
1.232(3)
1.442(3)
1.348(3)
1.356(3)
1.513(3)
1.714(2)
1.833(7)
2.225(4)
2.429(2)
1.171(8)
C(1)-O(1)
P(1)-M-P(2)
P(1)-M-H(01)
P(1)-M-C(1)
P(1)-M-O(2)
P(1)-M-S
P(2)-M-H(01)
P(2)-M-C(1)
P(2)-M-O(2)
P(2)-M-S
171.17(5)
169.83(2)
84.0(8)
88.62(7)
94.31(4)
90.06(2)
86.4(8)
87.25(7)
95.59(4)
92.39(2)
83.7(8)
175.1(8)
86.2(8)
C(1)-M-O(2)
99.6(2)
100.77(8)
169.98(7)
89.23(4)
110.12(8)
114.9(2)
113.6(2)
127.8(2)
111.2(2)
119.6(2)
129.3(2)
132.03(15)
C(1)-M-S
170.9(2)
89.49(12)
110.0(2)
114.8(5)
113.7(6)
127.7(6)
111.5(6)
118.8(6)
129.7(6)
131.5(4)
88.5(2)
93.72(13)
90.02(6)
O(2)-M-S
M-S-C(23)
S-C(23)-C(24)
C(22)-C(23)-C(24)
C(20)-C(22)-C(23)
C(22)-C(20)-O(3)
O(2)-C(20)-O(3)
C(22)-C(20)-O(2)
M-O(2)-C(20)
87.8(2)
94.80(13)
92.35(6)
H(01)-M-C(1)
H(01)-M-O(2)
H(01)-M-S
a
The first set of values (Os) corresponds to the bond distances and angles of the complex 8; the second set of values (Ru) corresponds
to the related parameters observed in complex 10.
Sch em e 2
Os-H bond to give the alkenyl derivative Os{C[C(O)-
OCH3]dCHCO2CH3}Cl(CO)(PiPr3)2.6c
3. Syn th esis a n d Ch a r a cter iza tion of F ive-Co-
or d in a te Alk en yl-Meta lloth iol Com p lexes. Phen-
ylacetylene and methylpropiolate, in contrast to acety-
lenedicarboxylic methyl ester, react with 3 and 4 by
insertion of the carbon-carbon triple bonds into the
M-H bonds of these compounds (eq 1). The five-
coordinate complexes Os{(E)-CHdCHPh}(SH)(CO)(Pi-
Pr3)2 (11), Ru{(E)-CHdCHPh}(SH)(CO)(PiPr3)2 (12), and
Ru{(E)-CHdCHCO2CH3}(SH)(CO)(PiPr3)2 (13), inor-
ganic counterpart of the organic R, â-unsaturated mer-
captans, formed are the first alkenyl-metallothiols
isolated.
Complexes 11-13 were prepared in 40-60% yield and
1
characterized by elemental analysis and IR and H, 13C-
{1H}, and 31P{1H} NMR spectroscopies. The presence
of an alkenyl group with E stereochemistry in these
compounds is strongly supported by the resonances of
the vinylic protons of the unsaturated η1-carbon ligands
in the 1H NMR spectra. The value of the coupling
constants between these protons (about 14 Hz for the
three derivatives) is characteristic for this arrange-
ment.12a Furthermore, the 1H NMR spectra show a
triplet between 1.49 and 3.42 ppm, with H-P coupling
constant values between 16.2 and 17.7 Hz, which was
assigned to the -SH proton. The multiplicity of these
resonances indicates that although the complexes are
F igu r e 2. Molecular diagram of complex RuH{SC(CO2-
CH3)CHC(OCH3)O}(CO)(PiPr3)2 (10).
insertion of the acetylene into the Pd-N bond.27 In
addition, we must point out the different behavior of 3
and its precursor 1, which reacts with acetylenedicar-
boxylic methyl ester by insertion of the alkyne in the

Five-Coordinate Complexes MHCl(CO)(PiPr3)2
Organometallics, Vol. 16, No. 26, 1997 5753
Calcd for C19H44OOsP2S: C, 39.84; H, 7.74; S, 5.60. Found:
C, 39.58; H, 7.50; S, 6.07.
unsaturated, they are also monomeric in solution, as
precursors 3 and 4. In addition, it should be noted that
the values of the H-P coupling constants are similar
to those found in 3 and 4, suggesting that in 11-13 the
disposition of the S-H bond could also be pseudo-parallel
to the P-M-P direction. As in 3 and 4, the 31P{1H}
NMR spectra show singlets at 21.2 (11), 41.4 (12), and
43.2 (13) ppm, indicating that the phosphine ligands
also become equivalent in solution.
In the 13C{1H} NMR spectra, the resonances of the
R-carbon atom of the alkenyl groups appear at 135.3
(11), 152.4 (12), and 186.4 (13) ppm, as triplets with
C-P coupling constants of 3.1 (11), 10.8 (12), and 10.2
(13) Hz. The resonances of the â-carbon atoms are
observed at 141.5 (11), 139.9 (12), and 126.2 (13) ppm,
also as triplets but with C-P coupling constants be-
tween 1 and 3 Hz.
IR (Nujol, cm-1): ν(Os-H) 1905; ν(CO) 1884. 1H NMR (300
MHz, C6D6): δ 4.14 (t, 1H, J H-P ) 18.7 Hz, Os-SH), 2.45 (m,
6H, PCHCH3), 1.22 (dvt, 36H, J H-H ) 6.9 Hz, N ) 13.4 Hz,
PCHCH3), -23.25 (t, 1H, J H-P ) 14.8 Hz, Os-H). 31P{1H}
NMR (121.42 MHz, C6D6): δ 44.6 (s).
P r ep a r a tion of Ru H(SH)(CO)(P iP r 3)2 (4). A solution of
RuHCl(CO)(PiPr3)2 (2) (1.10 g, 2.26 mmol) in THF/CH3OH (2:
1, 20 mL) was treated with NaSH (215 mg, 3.8 mmol). The
mixture was stirred for 7.5 h at room temperature. The
solution was concentrated to dryness; then 10 mL of toluene
was added, and the solution was filtered through Kieselguhr.
The filtrate was concentrated to ca. 0.5 mL; addition of
methanol caused the precipitation of an orange solid. The
solvent was decanted, and the solid was washed with methanol
and dried in vacuo. Yield: 725 mg (66%). Anal. Calcd for
C
19H44OP2RuS: C, 47.18; H, 9.17; S, 6.63. Found: C, 46.62;
H, 9.49; S, 6.57.
IR (Nujol, cm-1): ν(Ru-H) 2017; ν(CO) 1900. H NMR (300
MHz, C6D6): δ 2.35 (m, 6H, PCHCH3), 1.76 (t, 1H, J H-P ) 17.4
Hz, Ru-SH), 1.23 (dvt, 18H, J H-H ) 6.9 Hz, N ) 13.8 Hz,
PCHCH3), 1.21 (dvt, 18H, J H-H ) 7.2 Hz, N ) 12.9 Hz,
PCHCH3), -20.71 (t, 1H, J H-P ) 18.0 Hz, Ru-H). 31P{1H}
NMR (121.42 MHz, C6D6): δ 61.0 (s).
1
Con clu d in g Rem a r k s
This study has revealed that the five-coordinate
complexes MHCl(CO)(PiPr3)2 (M ) Os, Ru) are useful
starting materials for the preparation of new five- and
six-coordinate hydrido-metallothiol, six-coordinate mono-
thio-â-diketonato, and five-coordinate alkenyl-metal-
lothiol derivatives. Thus, they react with NaSH to
afford MH(SH)(CO)(PiPr3)2 (M ) Os, Ru), which are
novel precursors for the preparation of the above-
mentioned compounds.
P r ep a r a t ion of OsH(SH)(CO)2(P iP r 3)2 (5). CO was
bubbled through a stirred solution of OsH(SH)(CO)(PiPr3)2 (3)
(115 mg, 0.20 mmol) in 6 mL of diethyl ether for 10 min. The
solution was concentrated to dryness. After the addition of
pentane a white solid was formed. The solvent was decanted,
and the solid was washed with pentane, and dried in vacuo.
Yield: 106 mg (89%). Anal. Calcd for C20H44O2OsP2S: C,
39.99; H, 7.38; S, 5.34. Found: C, 39.92; H, 7.00; S, 5.63.
IR (Nujol, cm-1): ν(Os-H) 2052; ν(CO) 1972, 1907.1H NMR
(300 MHz, C6D6): δ 2.66 (m, 6H, PCHCH3) 1.19 (dvt, 18H, J H-H
) 7.5 Hz, N ) 14.4 Hz, PCHCH3), 1.17 (dvt, 18H, J H-H ) 7.2
Hz, N ) 14.1 Hz, PCHCH3), -2.46 (dt, 1H, J H-H ) 6.0 Hz,
J H-P ) 1.2 Hz, Os-SH) -6.65 (td, 1H, J H-P ) 21.0 Hz, J H-H
) 6.0 Hz, Os-H). 31P{1H} NMR (121.42 MHz, C6D6): δ 22.2
(s).
From a methodological point of view, the synthesis
of the monothio-â-diketonato complexes MH{SC(CO2-
CH3)CHC(OCH3O}(CO)(PiPr3)2 (M ) Os, Ru) as a result
of the unprecedented insertion of the carbon-carbon
triple bond of acetylenedicarboxylic methyl ester into
the S-H bond of MH(SH)(CO)(PiPr3)2 should be pointed
out. Phenylacetylene and methylpropiolate, in contrast
to the internal alkyne, react by insertion of the carbon-
carbon triple bond into the M-H bond to give M{(E)-
CHdCHR}(SH)(CO)(PiPr3)2 (M ) Os, Ru), which are the
first inorganic counterparts of the organic R,â-unsatur-
ated mercaptans.
P r ep a r a tion of Ru H(SH)(CO)2(P iP r 3)2 (6). CO was
bubbled through a stirred solution of RuH(SH)(CO)(PiPr3)2 (4)
(119 mg, 0.25 mmol) in 6 mL of pentane for 1 h. The mixture
was filtered through Kieselguhr, and then the resulting
solution was stored at -78 °C for 24 h. A white solid was
formed. The solvent was decanted, and the solid was washed
with pentane and dried in vacuo. Yield: 51.5 mg (41%). Anal.
Calcd for C20H44O2P2RuS: C, 46.95; H, 8.66; S, 6.26. Found:
C, 46.95; H, 8.61; S, 6.38.
Exp er im en ta l Section
All reactions were carried out under an argon atmosphere
using standard Schlenk techniques. Solvents were dried using
appropriate drying agents and freshly distilled under argon
before use. 1H, 31P{1H}, and 13C{1H} NMR spectra were
recorded on either a Varian Unity 300 or on a Bruker 300 AXR
spectrometer. Chemical shifts are expressed in ppm upfield
from Me4Si (1H and 13C) and 85% H3PO4 (31P). Coupling
constants (J and N [N ) J (PH) + J (P′H) or J (PC) + J (P′C)])
are given in hertz. IR data were recorded on a Nicolet 550
spectrophotometer. Elemental analyses were carried out with
a Perkin-Elmer 240C microanalyzer. The starting complexes
OsHCl(CO)(PiPr3)2 and RuHCl(CO)(PiPr3)2 were prepared by
published methods.5
P r ep a r a tion of OsH(SH)(CO)(P iP r 3)2 (3). A solution of
OsHCl(CO)(PiPr3)2 (1) (470 mg, 0.82 mmol) in THF/CH3OH
(4:1, 15 mL) was treated with NaSH (150 mg, 2.7 mmol). The
color of the solution changed immediately from red to dark
orange. The mixture was stirred for 5 min at room temper-
ature. The solution was concentrated to dryness; then 15 mL
of toluene was added, and the solution was filtered through
Kieselguhr. The filtrate was concentrated to ca. 0.5 mL;
addition of pentane caused the precipitation of an orange solid.
The solvent was decanted, and the solid was washed with
pentane and dried in vacuo. Yield: 393 mg (83%). Anal.
IR (Nujol, cm-1): ν(Ru-H) 2018; ν(CO) 1955, 1910. 1H NMR
(300 MHz, C6D6): δ 2.62 (m, 6H, PCHCH3), 1.20 (dvt, 36H,
J H-H ) 7.2 Hz, N ) 14.1 Hz, PCHCH3), -2.96 (dt, 1H, J H-H
)
4.5 Hz, J H-P ) 1.5 Hz, Ru-SH), -6.14 (td, 1H, J H-P ) 20.7
Hz, J H-H ) 4.5 Hz, Ru-H). 31P{1H} NMR (121.42 MHz,
C6D6): δ 57.8 (s).
P r ep a r a tion of OsH(SH)(CO){P (OMe)3}(P iP r 3)2 (7). A
solution of OsH(SH)(CO)(PiPr3)2 (3) (95 mg, 0.16 mmol) in 5
mL of THF was treated with P(OMe)3 (20 µL, 0.17 mmol). The
mixture was stirred for 15 min. The solution was concentrated
to dryness. After the addition of pentane, a white solid was
formed. The solvent was decanted, and the solid was washed
with pentane and dried in vacuo. Yield: 90 mg (78%). Anal.
Calcd for C22H53O4OsP3S: C, 37.92; H, 7.67; S, 4.60 Found:
C, 37.56; H, 7.74; S, 4.85.
IR (Nujol, cm-1): ν(Os-H) 2065; ν(CO) 1918. 1H NMR (300
MHz, C6D6): δ 3.35 (d, 9H, J H-P ) 10.5 Hz, POCH3), 2.88 (m,
6H, PCHCH3), 1.33 (dvt, 18H, J H-H ) 7.2 Hz, N ) 13.2 Hz,
PCHCH3), 1.31 (dvt, 18H, J H-H ) 6.0 Hz, N ) 12.8 Hz,
PCHCH3), -2.40 (dd, 1H, J H-P′ ) 18.6 Hz, J H-H ) 5.1 Hz, Os-
SH), -8.39 (dtd, 1H, J H-P′ ) 137.1 Hz, J H-P ) 25.6 Hz, J H-H
) 5.1 Hz, Os-H). 31P{1H} NMR (121.42 MHz, C6D6): δ 102.2
(t, J P-P ) 18.0 Hz), 13.5 (d, J P-P ) 18.0 Hz).

5754 Organometallics, Vol. 16, No. 26, 1997
Buil et al.
Ta ble 2. Cr ysta l Da ta a n d Da ta Collection a n d
P r ep a r a tion of OsH[SC(CO2CH3)CHC(OCH3)O}(CO)-
(P iP r 3)2 (8). A solution of OsH(SH)(CO)(PiPr3)2 (3) (135.0 mg,
0.24 mmol) in 8 mL of THF was treated with acetylenedicar-
boxylic methyl ester (30 µL, 0.24 mmol). The mixture was
stirred for 2 h. The solution was concentrated to dryness. After
the addition of pentane, a red solid was formed. The solvent
was decanted, and the solid was washed with pentane and
Refin em en t for
OsH{SC(CO2CH3)CHC(OCH3)O}(CO)(P iP r 3)2 (8) a n d
Ru H{SC(CO2CH3)CHC(OCH3)O}(CO)(P iP r 3)2 (10)
8
10
formula
mol wt
C25H50O5OsP2S
714.85
C25H50O5P2RuS
625.72
dried in vacuo. Yield: 145 mg (86%). Anal. Calcd for C25H50
-
color, habit
crystal size, mm
space group
a, Å
b, Å
c, Å
red, laminar crystal orange, irregular block
O5OsP2S: C, 42.00; H, 7.05; S, 4.49. Found: C, 41.57; H, 7.04;
S, 4.96.
0.52 × 0.12 × 0.06
triclinic, P1h
8.5239(9)
11.9327(14)
15.171(2)
94.565(10)
97.941(8)
93.184(6)
1520.0(4)
2
0.44 × 0.28 × 0.26
triclinic, P1h
8.5583(8)
11.9282(11)
15.2736(13)
94.569(8)
97.478(9)
92.724(9)
1538.4(3)
2
IR (Nujol, cm-1): ν(Os-H) 2177; ν(CO) 1895; ν(CdO) 1716.
1H NMR (300 MHz, C6D6): δ 7.11 (s, 1H, -CH-), 3.30 and
3.35 (both s, each 3H, CO2CH3), 2.62 (m, 6H, PCHCH3), 1.23
(dvt, 18H, J H-H ) 6.6 Hz, N ) 12.9 Hz, PCHCH3), 1.12 (dvt,
18H, J H-H ) 6.3 Hz, N ) 12.6 Hz, PCHCH3), -20.26 (t, 1H,
J H-P ) 16.2 Hz, Os-H). 13C{1H} NMR (75.43 MHz, C6D6): δ
185.7 (t, J C-P ) 10.1 Hz, OsCO), 168.0 and 167.3 (both s, CO2-
CH3), 166.1 (s, SC(CO2CH3)), 111.6 (s, -CH-), 52.2 and 51.7
(both s, CO2CH3), 25.7 (vt, N ) 24.4 Hz, PCHCH3), 19.5 and
19.2 (both s, PCHCH3). 31P{1H} NMR (121.42 MHz, C6D6): δ
22.7 (s, d under off-resonance conditions).
R, deg
â, deg
γ, deg
V, Å3
Z
D(calcd), g cm-3
1.562
1.351
µ, mm-1
4.399
0.712
scan type
2θ range, deg
temp, K
θ/2θ
2.7 e 2θ e 50
200
θ/2θ
4.2 e 2θ e 50
173
no. of data collected
no. of unique data
7337
6564
P r ep a r a tion of Ru H{SC(CO2CH3)CHC(OCH3)O}(CO)-
(P iP r 3)2 (9). A solution of RuH(SH)(CO)(PiPr3)2 (4) (176.4 mg,
0.36 mmol) in 6 mL of pentane was treated with acetylenedi-
carboxylic methyl ester (53.7 µL, 0.44 mmol). After the
mixture was stirred for 5 h, a deep red solid was formed. The
solvent was decanted, and the solid was washed twice with
pentane and dried in vacuo. Yield: 73.5 mg (32%). Anal.
Calcd for C25H50O5P2RuS: C, 47.99; H, 8.05; S, 5.12. Found:
C, 47.66; H, 7.52; S, .5.51.
IR (Nujol, cm-1): ν(Ru-H) 2025; ν(CO) 1908; ν(CdO) 1716.
1H NMR (300 MHz, C6D6): δ 6.99 (s, 1H, -CH-), 3.39 and
3.19 (both s, each 3H, CO2CH3), 2.20 (m, 6H, PCHCH3), 1.28
(dvt, 18H, J H-H ) 6.9 Hz, N ) 12.9 Hz, PCHCH3), 1.24 (dvt,
18H, J H-H ) 7.2 Hz, N ) 13.2 Hz, PCHCH3), -9.16 (t, 1H,
J H-P ) 19.5 Hz, Ru-H). 13C{1H} NMR (75.43 MHz, C6D6): δ
207.9 (t, J C-P ) 14.3 Hz, RuCO), 174.9 and 170.0 (both s, CO2-
CH3), 167.0 (s, SC(CO2CH3)), 107.3 (s, -CH-), 52.1 and 51.1
(both s, CO2CH3), 25.1 (vt, N ) 18.4 Hz, PCHCH3), 19.5 and
19.1 (both s, PCHCH3). 31P{1H} NMR (121.42 MHz, C6D6): δ
54.0 (s, d under off-resonance conditions).
5327 (Rint ) 0.0471) 5381 (Rint ) 0.0152)
no. of params refined 322
326
a
R1 (Fo g 4.0σ(Fo))
0.0382
0.1093
0.983
0.0225
0.0585
0.963
b
wR2 (all data)
Sc
a
b
2
R1(F) ) Σ||Fo| - |Fc||/Σ|Fo|. wR2(F2) ) [Σ[w(Fo - Fc2)2]/
Σ[w(Fo2)2]]1/2; w-1 ) [σ2(Fo2)+ (aP)2 + bP], where P ) [max(Fo2, 0)
+ 2Fc2)]/3 (8, a ) 0.0827, b ) 1.01; 10, a ) 0.0394, b ) 0.01). c S
) [Σ[w(Fo2 - Fc2)2]/(n - p)]1/2, where n is the number of reflections
and p the number of parameters.
MHz, C6D6): δ 8.68 (d, 1H, J H-H ) 13.8 Hz, OssCHd), 7.30-
6.90 (m, 5H, C6H5), 6.29 (d, 1H, J H-H ) 13.8 Hz, dCHPh), 3.42
(t, 1H, J H-P ) 17.7 Hz, Os-SH), 2.61 (m, 6H, PCHCH3), 1.21
(dvt, 18H, J H-H ) 6.6 Hz, N ) 13.5 Hz, PCHCH3); 1.14 (dvt,
18H, J H-H ) 6.3 Hz, N ) 12.9 Hz, PCHCH3). 13C{1H} NMR
(75.43 MHz, C6D6): δ 188.3 (t, J C-P ) 9.2 Hz, Os-CO), 141.5
(t, J C-P ) 1.7 Hz, Os-CHdC); 135.3 (t, J C-P ) 3.1 Hz, Os-
CHdC), 128.7, 124.3. 124.0 (all s, C6H5), 25.4 (vt, N ) 24.9
Hz, PCHCH3); 20.2 and 19.5 (both s, PCHCH3). 31P{1H} NMR
(121.42 MHz, C6D6): δ 21.2 (s).
P r ep a r a tion of Ru H{SC(CO2CH3)CHC(OCH3)O}(CO)-
(P iP r 3)2 (10). A solution of 9 (102.5 mg, 0.16 mmol) in 5 mL
of toluene was stirred for 15 min. The solution was concen-
trated to dryness. After the addition of methanol, an orange
solid was formed. The solvent was decanted, and the orange
solid was washed with methanol and dried in vacuo. Yield:
46 mg (45%). Anal. Calcd for C25H50O5P2RuS: C, 47.99; H,
8.05; S, 5.12. Found: C, 47.80; H, 8.15; S, 5.61.
P r ep a r a t ion of R u {(E)-CHdCHP h }(SH)(CO)(P iP r 3)2
(12). A solution of RuH(CO)(SH)(PiPr3)2 (4) (102 mg, 0.21
mmol) in 6 mL of pentane was treated with PhCtCH (25.8
µL, 0.25 mmol). After the mixture was stirred for 1.5 min, a
dark orange solid was formed. The solvent was decanted, and
the solid was washed with pentane and dried in vacuo.
Yield: 78 mg (63%). Anal. Calcd for C27H50OP2RuS: C, 55.36;
H, 8.60; S, 5.47. Found: C, 54.81; H, 8.82; S, 5.76.
IR (Nujol, cm-1): ν(Ru-H) 2080; ν(CO) 1909; ν(CdO) 1717.
1H NMR (300 MHz, C6D6): δ 7.01 (s, 1H, -CH-), 3.36 and
3.32 (both s, each 3H, CO2CH3), 2.57 (m, 6H, PCHCH3), 1.25
(dvt, 18H, J H-H ) 6.7 Hz, N ) 13.3 Hz, PCHCH3); 1.13 (dvt,
18H, J H-H ) 6.6 Hz, N ) 12.9 Hz, PCHCH3); -17.88 (t, 1H,
J H-P ) 20.1 Hz, Ru-H). 13C{1H} NMR (75.43 MHz, C6D6): δ
203.4 (t, J C-P ) 13.8 Hz, Ru-CO), 169.8 and 169.1 (both s, CO2-
CH3), 167.4 (s, SC(CO2CH3)), 110.4 (s, -CH-), 52.0 and 51.1
(both s, CO2CH3), 25.5 (vt, N ) 19.6 Hz, PCHCH3), 19.5 and
19.2 (both s, PCHCH3). 31P{1H} NMR (121.42 MHz, C6D6): δ
47.5 (s, d under off-resonance conditions).
IR (Nujol, cm-1): ν(CO) 1894; ν(CdC) 1595. 1H NMR (300
MHz, C6D6): δ 8.94 (d, 1H, J H-H ) 13.8 Hz, RusCHd), 7.28-
6.9 (m, 5 H, C6H5), 6.46 (d, 1H, J H-H ) 13.8 Hz, dCHPh), 2.50
(m, 6H, PCHCH3), 1.49 (t, 1H, J H-P ) 16.2 Hz, Ru-SH), 1.19
and 1.14 (both dvt, 18H, J H-H ) 7.2 Hz, N ) 13.2 Hz,
PCHCH3). 13C{1H} NMR (75.43 MHz, C6D6): δ 205.4 (t, J C-P
) 13.1 Hz, Ru-CO), 152.4 (t, J C-P ) 10.8 Hz, Ru-CHdC),
139.9 (t, J C-P ) 2.1 Hz, Ru-CHdC), 135.6 (t, J C-P ) 3.5 Hz,
Cipso-Ph), 128.9 (s, Cortho-Ph); 124.31 (s, Cmeta-Ph), 124.26 (s,
Cpara-Ph), 25.2 (vt, N ) 19.8 Hz, PCHCH3), 20.2 and 19.5 (both
s, PCHCH3). 31P{1H} NMR (121.42 MHz, C6D6): δ 41.4 (s).
P r ep a r a t ion of R u {(E)-CH dCH CO2CH 3}(SH )(CO)-
(P iP r 3)2 (13). A solution of RuH(CO)(SH)(PiPr3)2 (4) (78.3 mg,
016 mmol) in 6 mL of pentane was treated with HCtCCO2-
CH3 (15.2 µL, 0.18 mmol). After the mixture was stirred for
1 h, a yellow solid was formed. The solvent was decanted, and
the yellow solid was washed with pentane and dried in vacuo.
Yield: 40 mg (44%). Anal. Calcd for C27H50O3P2RuS: C,
48.80; H, 8.52; S, 5.60. Found: C, 49.20; H, 8.78; S, 5.61.
IR (Nujol, cm-1): ν(CO) 1909; ν(CdO) 1693; ν(CdC) 1520.
1H NMR (300 MHz, C6D6): δ 10.65 (dt, 1H, J H-H ) 13.5 Hz,
P r epar ation of Os{(E)-CHdCHP h }(SH)(CO)(P iP r 3)2 (11).
A solution of OsH(CO)(SH)(PiPr3)2 (3) (120 mg, 0.21 mmol) in
6 mL of diethyl ether was treated with PhCtCH (23 µL, 0.21
mmol). The mixture was stirred for 20 min. The solution was
concentrated to dryness, and after the addition of pentane, a
dark orange solid was formed. The solvent was decanted, and
the solid was washed with pentane and dried in vacuo.
Yield: 78 mg (55%). Anal. Calcd for C27H50OOsP2S: C, 48.05;
H, 7.47; S, 4.75. Found: C, 47.61; H, 7.83; S, 5.01.
IR (Nujol, cm-1): ν(CO) 1881; ν(CdC) 1550. 1H NMR (300

Five-Coordinate Complexes MHCl(CO)(PiPr3)2
Organometallics, Vol. 16, No. 26, 1997 5755
J H-P ) 1.0 Hz, Ru-CHdC), 6.34 (dt, 1H, J H-H ) 13.5 Hz, J H-P
) 1.8 Hz, -CHdCH), 3.55 (s, 3H, -CO2CH3), 2.42 (m, 6H,
PCHCH3), 1.58 (t, 1H, J H-P ) 16.5 Hz, Ru-SH), 1.14 (dvt, 18H,
J H-H ) 7.2 Hz, N ) 13.8 Hz, PCHCH3), 1.09 (dvt, 18H, J H-H
) 6.9 Hz, N ) 14.0 Hz, PCHCH3). 13C{1H} NMR (75.43 MHz,
by least-squares methods. Three standard reflections were
monitored at periodic intervals thoughout data collection: no
significant variations were observed. All data were corrected
for absorption using a semiempirical method.28 The structures
were solved by Patterson (Os atom, SHELXTL-PLUS29) (8) or
direct methods (10) and conventional Fourier techniques and
refined by full-matrix least-squares on F2 (SHELXL9330).
Anisotropic parameters were used in the last cycles of refine-
ment for all non-hydrogen atoms. The hydrogen atoms were
observed (hydrido in 10) or calculated and refined riding on
carbon atoms with common isotropic thermal parameters.
Atomic scattering factors, corrected for anomalous dispersion
for Os, Ru, and P, were implemented by the program. The
refinement converge to R1 [F2 > 2σ(F2)] ) 0.0382 (8) or 0.0225
(10) and wR2 (all data) ) 0.1093 (8) or 0.0585 (10).
C6D6): δ 204.3 (t, J C-P ) 12.4 Hz, Ru-CO), 186.4 (t, J C-P
)
10.2 Hz, Ru-CHdCH), 162.4 (t, J C-P ) 1.6 Hz, -CO2CH3),
126.2 (t, J C-P ) 2.8 Hz, Ru-CHdC), 50.1 (s, -CO2CH3), 25.3
(vt, N ) 20.2 Hz, PCHCH3), 20.1 and 19.4 (both s, PCHCH3).
31P{1H} NMR (121.42 MHz, C6D6): δ 43.2 (s).
Cr ysta l Da ta for 8 a n d 10. Crystals suitable for the X-ray
diffraction study were grown in a solution of complex 8 in
pentane (or 10 in acetone) after storing at -20 °C for 3 days
(or at 0 °C for 1 week (10)). A summary of the crystal data
and refinement parameters is reported in Table 2. The red
(8) or orange (10) crystals (0.52 × 0.12 × 0.06 mm (8) and
0.44 × 0.28 × 0.26 mm (10)) were glued on a glass fiber and
mounted on a Siemens P4 four-circle diffractometer, with
graphite-monochromated Mo KR radiation. A group of 56
reflections in the range 24° e 2θ e 39° (8) or 52 reflections in
the range 30° e 2θ e 45° (10) were carefully centered at 200
(8) or 173 K (10) and used to obtain the unit cell dimensions
Ack n ow led gm en t. We thank the DGICYT (Project
No. PB95-0806, Programa de Promocio´n General del
Conocimiento) for financial support.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray study, and bond distances and angles for 8 and 10 (16
pages). Ordering information is given on any current mast-
head page.
(28) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr.
1968, A24, 351.
(29) Sheldrick, G. M. SHELXTL-PLUS; Siemens Analitical X-ray
Instruments, Inc.: Madison WI, 1990.
(30) Sheldrick, G. M. SHELXL-93; Program for Crystal Structure
Refinement; University of Go¨ttingen: Go¨ttingen, Germany, 1993.
OM970633V