Synthesis and characterization of [OsCl2(=C=CHR)(PPh 3)2] and related complexes

Article abstract of DOI:10.1002/ejic.200400003

Treatment of [OsCl₂(PPh₃)₃] with HC≡CR (R = Ph, p-tolyl, CMe₃) in the presence of HCl gives the corresponding trichloro(carbyne) complexes [OsCl₃(≡CCH ₂R)(PPh₃)₂] in g

Full text of DOI:10.1002/ejic.200400003

FULL PAPER
Synthesis and Characterization of [OsCl2(؍C؍CHR)(PPh3)2]
and Related Complexes
Ting Bin Wen,[a] Wai Yiu Hung,[a] Zhong Yuan Zhou,[b] Man Fung Lo,[a] Ian D. Williams,[a]
and Guochen Jia*[a]
Keywords: Carbyne ligands / Osmium / Vinylidene ligands
Treatment of [OsCl2(PPh3)3] with HCϵCR (R = Ph, p-tolyl,
CMe3) in the presence of HCl gives the corresponding tri-
and react with H2O to give (aqua)(vinylidene) complexes
[OsCl2(H2O)(=C=CHR)(PPh3)2]. The structures of several of
chloro(carbyne) complexes [OsCl3(ϵCCH2R)(PPh3)2] in good these new complexes have been determined by X-ray dif-
yields. The vinylidene complexes [OsCl2(=C=CHR)(PPh3)2]
(R = Ph, p-tolyl, CMe3) are, in turn, prepared from the reac-
tions of the carbyne complexes [OsCl3(ϵCCH2R)(PPh3)2]
with NEt3. These new vinylidene complexes are hygroscopic
fraction studies.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Prompted by the facile preparation of the (vinylidene)ru-
thenium complex [RuCl2(ϭCϭCHCMe3)(PPh3)2] from the
reaction of HCϵCCMe3 with [RuCl2(PPh3)3], we have at-
tempted to prepare analogous (vinylidene)osmium com-
plexes [OsCl2(ϭCϭCHR)(PPh3)2] from the reactions of
[OsCl2(PPh3)3] with HCϵCR. However, it was found that
(Vinylidene)ruthenium complexes[1] of the type [RuCl2-
(ϭCϭCHR)(PRЈ3)2] have attracted attention because they
are catalytically active for olefin metathesis,[2aϪ2c] dimeriz-
ation and carboxylation of terminal alkynes,[2d] and they
can be used as precursors to other vinylidene com-
plexes.[2d,2e] A number of such complexes have been pre-
pared from the reactions of HCϵCR with dichloro-
ruthenium complexes such as [RuCl2(PPh3)3],[3,4]
the
expected
vinylidene
complexes
[OsCl2(ϭCϭ
CHR)(PPh3)2] could not be isolated from the reactions of
[OsCl2(PPh3)3] with HCϵCR (R ϭ CMe3,[22] SiMe3 [23]).
Instead, the reactions afford a series of complexes including
carbyne complexes [OsCl3(ϵCCH2R)(PPh3)2], osmaben-
zyne complexes, and vinyl(vinylidene) complexes
[RuCl2H2(PRЈ3)2] (RЈ ϭ Cy, iPr),[5] [RuCl2(PiPr3)2]n,[6]
[6]
[RuCl2(MeCN)2(PiPr3)2],[6]
[RuCl2(p-cymene)]2/PRЈ3
[OsX{C(CϵCR)ϭCHR}(ϭCϭCHR)(PPh3)2] (X
ϭ Cl,
CϵCR).[22,23] It was suggested that these complexes are
formed via vinylidene intermediates [OsCl2(ϭCϭ
CHR)(PPh3)2], although attempts to isolate them from the
reactions failed. In this report, we will show that the vinyl-
idene complexes [OsCl2(ϭCϭCHR)(PPh3)2] can be ob-
tained from the deprotonation reactions of (carbyne)os-
mium complexes [OsCl3(ϵCCH2R)(PPh3)2].
and [{RuCl2(TPPMS)2}Na2]2·4H2O [TPPMS ϭ Ph2P(2-
OSO2C6H4)Na][7] or from the reaction of [RuCl2-
(ϭCHPh)(PCy3)2] with 1,2-propadiene.[2a]
In contrast to ruthenium, the chemistry of related (vinyl-
idene)osmium complexes of the type [OsCl2(ϭCϭ
CHR)(PRЈ3)2] is still underdeveloped, despite the fact that
a large number of other (vinylidene)osmium complexes
have been prepared.[8Ϫ21] To the best our knowledge, only
[OsCl2(ϭCϭCHPh)(PiPr3)2], which was produced by elim-
ination of the imine ligands from the (imine)(vinylidene)
complexes [OsCl2(ϭCϭCHPh)(NHϭCR2)(PiPr3)2] [CR2 ϭ
CMe2, C(CH2)5] in refluxing toluene, has been reported by
Esteruelas and co-workers.[13]
Results and Discussion
Preparation of Carbyne Complexes
[OsCl3(ϵCCH2R)(PPh3)2]
We have previously shown that the carbyne complexes
[OsCl3(ϵCCH2CMe3)(PPh3)2] (4) and [OsCl3(ϵCCH3)-
(PPh3)2] (5) are formed as one of the products from the
reaction of [OsCl2(PPh3)3] (1) with HCϵCCMe3 and
HCϵCSiMe3, respectively.[22,23] It was suspected that the
carbyne complexes were produced by protonation of the vi-
nylidene intermediates [OsCl2(ϭCϭCHR)(PPh3)2] with
HCl generated in situ. Thus, it was expected that carbyne
[a]
Department of Chemistry and Open Laboratory of
Chirotechnology of the Institute of Molecular Technology for
Drug Discovery and Synthesis, The Hong Kong University of
Science and Technology,
Clear Water Bay, Kowloon, Hong Kong, P. R. China
[b]
Department of Applied Biology and Chemical Technology,
Hong Kong Polytechnic University,
Kowloon, Hong Kong, P. R. China
Eur. J. Inorg. Chem. 2004, 2837Ϫ2846
DOI: 10.1002/ejic.200400003
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T. B. Wen, W. Y. Hung, Z. Y. Zhou, M. F. Lo, I. D. Williams, G. Jia
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complexes [OsCl3(ϵCCH2R)(PPh3)2] might be readily pre- δ ϭ 1.77 (for 2) and 1.72 ppm (for 3). The 13C{1H} NMR
pared from the reaction of [OsCl2(PPh3)3] (1) with HCϵCR spectra (in CD2Cl2) exhibit the resonances of the C-α atoms
in the presence of HCl. Indeed, treatment of [OsCl2(PPh3)3] of the carbyne ligands as a triplet at δ ϭ 278.2 (2) and
(1) with HCϵCR (R ϭ Ph, p-tolyl, CMe3) and HCl gave 280.1 ppm (3) and the signals of the CH2 carbon atoms as
exclusively the corresponding (carbyne)trichloro complexes a singlet at δ ϭ 57.3 (2) and 57.1 ppm (3). The 31P{1H} and
[OsCl3(ϵCCH2R)(PPh3)2] (2Ϫ4) in good yields [Equa- 13C{1H} NMR spectroscopic data suggest that the two
tion (1)].
PPh3 ligands in 2 and 3 are trans to each other and that the
carbyne ligand is trans to a chloro ligand.
The structure of 2 was confirmed by an X-ray diffraction
study. A view of the molecular geometry of 2 is shown in
Figure 1. Selected bond lengths and angles are given in
Table 1. Similarly to 4,[22] the geometry around the osmium
atom in 2 can be viewed as a distorted octahedron with two
PPh3 ligands at the axial positions and the three chlorides
and the carbyne ligand in the equatorial plane. The
OsϪC(1)ϪC(2) unit in 2 is almost linear with a bond angle
(1)
The analogous reaction of 1 with HCϵCSiMe3 in the
presence of HCl led to the known desilylated (carbyne)-
trichloro complex [OsCl3(ϵCCH3)(PPh3)2] (5), which was
isolated as a yellow solid in 71% yield [Equation (2)]. It is
assumed that reaction of 1 with HCϵCSiMe3 initially gen-
erates the vinylidene intermediate [OsCl2(ϭCϭCHSi-
Me3)(PPh3)2], which reacts with HCl to give the (carbyne)-
trichloro complex [OsCl3(ϵCCH2SiMe3)(PPh3)2]. Desilyl-
ation of the later carbyne complex by electrophilic reagents
(e.g. HCl or H2O) produces the carbyne complex 5. There
are many reports on the cleavage of SiϪC bonds by H2O
or acids to give CϪH bonds.[24Ϫ27]
of 174.8(3)°. The OsϪC(carbyne) bond length in 2 [1.734(3)
[22]
˚
˚
A] is nearly identical to that in 4 [1.728(3) A],
and is
within the range of those reported previously for other (car-
byne)osmium complexes.[10,16,18,22,24,25,27Ϫ34] As expected,
˚
the OsϪCl(1) bond [2.4621(8) A] is significantly longer than
˚
the mutually trans bonds OsϪCl(2) [2.4105(7) A] and
(2)
The new complexes 2 and 3 were characterized by multi-
nuclear NMR spectroscopy. The 31P{1H} NMR spectra (in
CDCl3) of complexes 2 and 3 display singlet 31P signals at
δ ϭ Ϫ12.9 and Ϫ12.1 ppm, respectively. The 1H NMR
spectra (in CDCl3) display the ϵCCH2 proton signals at Figure 1. Molecular structure for [OsCl3(ϵCCH2Ph)(PPh3)2] (2)
˚
Table 1. Selected bond lengths [A] and bond angles [°] for [OsCl3(ϵCCH2Ph)(PPh3)2]·1.5C6H6 (2·1.5C6H6) and
[OsCl3(ϵCCH3)(PPh3)2]·CH2Cl2 (5·CH2Cl2)
2
5
2
5
Os(1)ϪC(1)
Os(1)ϪP(1)
Os(1)ϪCl(1)
Os(1)ϪCl(3)
1.734(3)
1.724(5)
C(1)ϪC(2)
Os(1)ϪP(2)
Os(1)ϪCl(2)
C(2)ϪC(3)
1.457(5)
2.4339(8)
2.4105(7)
1.515(5)
1.434(7)
2.4426(14)
2.3845(13)
2.4501(8)
2.4621(8)
2.3874(8)
2.4476(14)
2.4827(13)
2.4227(14)
P(2)ϪOs(1)ϪP(1)
C(1)ϪOs(1)ϪCl(1)
P(1)ϪOs(1)ϪCl(1)
Cl(2)ϪOs(1)ϪP(1)
Cl(3)ϪOs(1)ϪP(1)
Cl(2)ϪOs(1)ϪCl(1)
C(1)ϪOs(1)ϪP(1)
C(1)ϪOs(1)ϪCl(2)
C(1)ϪC(2)ϪC(3)
175.83(3)
176.16(4)
Cl(3)ϪOs(1)ϪCl(2)
C(2)ϪC(1)ϪOs(1)
P(2)ϪOs(1)ϪCl(1)
Cl(2)ϪOs(1)ϪP(2)
Cl(3)ϪOs(1)ϪP(2)
Cl(3)ϪOs(1)ϪCl(1)
C(1)ϪOs(1)ϪP(2)
C(1)ϪOs(1)ϪCl(3)
170.77(3)
178.56(5)
173.84(10)
92.46(3)
86.72(3)
92.21(3)
88.81(3)
89.87(10)
97.02(10)
111.1(3)
175.40(17)
89.57(5)
87.41(5)
91.84(5)
88.65(5)
91.32(17)
94.44(18)
174.8(3)
84.71(3)
90.16(3)
90.43(3)
82.07(3)
93.26(10)
92.14(10)
174.0(5)
87.86(5)
89.74(5)
90.96(5)
90.12(5)
91.47(17)
86.81(18)
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[OsCl2(ϭCϭCHR)(PPh3)2] and Related Complexes
FULL PAPER
˚
OsϪCl(3) [2.3874(8) A], due to the strong trans influence trichloro complexes 2Ϫ4 were readily deprotonated by
of the carbyne ligand.
NEt3 to give the corresponding moisture-sensitive dichloro-
The structure of 5 has been previously assigned on the (vinylidene) complexes 6Ϫ8, which can be isolated in good
basis of NMR spectroscopic data.[23] Its structure was now to excellent yields [Equation (3)].
also confirmed by an X-ray diffraction study. A view of the
molecular geometry of 5 is shown in Figure 2. Selected
bond lengths and angles are given in Table 1. Overall, the
structural features of 5 are similar to those of 2 and 4.
(3)
Our attempt to isolate the vinylidene complex [OsCl2-
(ϭCϭCH2)(PPh3)2] from the deprotonation reaction of the
(carbyne)trichloro complex [OsCl3(ϵCCH3)(PPh3)2] (5)
failed, however. The in situ 31P{1H} NMR spectrum for the
reaction of 5 with NEt3 in CD2Cl2 also showed a new broad
peak at δ ഠ 3.7 ppm, which is similar to those observed for
the in situ reactions of [OsCl3(ϵCCH2R)(PPh3)2] (R ϭ Ph
or p-tolyl, CMe3) with NEt3, indicative of the formation of
the vinylidene complex [OsCl2(ϭCϭCH2)(PPh3)2]. How-
ever, after workup with a procedure similar to that used for
the isolation of 6Ϫ8, the isolated solid showed the 31P{1H}
NMR signal of 5 and several unidentified broad peaks. Ap-
parently, the initially formed vinylidene complex decom-
Figure 2. Molecular structure for [OsCl3(ϵCCH3)(PPh3)2] (5)
poses during workup.
The solid-state structure of the vinylidene complex 8 was
determined by an X-ray diffraction study. A view of the
molecular geometry of 8 is shown in Figure 3. Selected
bond lengths and angles are given in Table 2. The geometry
around the osmium atom in 8 may be described as a dis-
torted trigonal bipyramid with two PPh3 ligands at the axial
positions and the other three ligands in the equatorial
plane. The deviation is reflected by the P(1)ϪOsϪP(2) angle
[168.13(2)°] (which is bent away from the vinylidene ligand)
and the Cl(1)ϪOsϪCl(2) angle [149.31(2)°]. The
ClϪOsϪCl angle is close to that calculated for the model
complex [OsCl2(ϭCϭCH2)(PH3)2] (146.9°)[40] and the
XϪMϪX angles observed in the analogous compounds
The chemistry of (carbyne)osmium complexes has re-
ceived considerable attention, especially in recent
years.[8,10,13,15Ϫ19,20a,20c,20d,20e,21Ϫ25,28Ϫ38] Reported com-
pounds closely related to 2Ϫ5 include [OsCl3(ϵCPh)-
(PPh3)2],[35]
[OsCl2(SCN)(ϵCC6H4NMe2)(PPh3)2],[35]
[OsHCl2(ϵCRЈ)(PR3)2] (R ϭ Cy, iPr),[19,24,25,36] [OsH-
Cl(OPh)(ϵCMe)(PiPr3)2],[19]
and [OsCl2(ϵCϪCHϭ
CRPh)[P(iPr)2CH2CO2Me)[P(iPr)2CH2CO2)] (R Ph,
ϭ
Me).[34] The analogous carbyne complex [OsCl3-
(ϵCPh)(PPh3)2] was previously obtained from the reaction
of HCl with [OsCl(ϵCPh)(O2CO)(PPh3)2], which was in
turn prepared from the reaction of [OsCl(ϵCPh)-
(CO)(PPh3)2] with O2.[35b] Thus, the reactions reported here
represent a much simpler route to (carbyne)osmium com-
plexes of the type [OsX3(ϵCRЈ)(PR3)2] (X ϭ halide).
Preparation of Vinylidene Complexes [OsCl2(؍C؍CHR)-
(PPh3)2]
Deprotonation of (carbyne)metal complexes is one of the
common routes to prepare vinylidene complexes. For ex-
ample, deprotonation of [CpOsH(ϵCCH2Ph)[P(iPr3)]BF4,
[OsH(OAc)(ϵCCH3)(PiPr3)2]BF4,
[OsHCl2(ϵCCH2Ph)-
(PiPr3)2], and [CpMn(ϵCCH3)(CO)2]BCl4 produces the
vinylidene complexes [CpOsH(ϭCϭCHPh)(PiPr3)],[17]
[OsH(OAc)(ϭCϭCH2)(PiPr3)2],[21] [OsHCl(ϭCϭCHPh)-
(PiPr3)2][37] and [CpMn(ϭCϭCH2)(CO)2],[39] respectively.
Thus, it was reasoned that the vinylidene complexes
[OsCl2(ϭCϭCHR)(PPh3)2] might be obtained by treatment
of the easily accessible (carbyne)trichloro complexes
[OsCl3(ϭCCH2R)(PPh3)2] with bases. Indeed, the (carbyne)- (8)
Figure 3. Molecular structure for [OsCl2(ϭCϭCHCMe3)(PPh3)2]
Eur. J. Inorg. Chem. 2004, 2837Ϫ2846
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T. B. Wen, W. Y. Hung, Z. Y. Zhou, M. F. Lo, I. D. Williams, G. Jia
FULL PAPER
[RuBr2(ϭCϭCHCMe3)(PPh3)2]
[144.81(7)°][3b]
and idene ligands at δ ϭ 280.8 and 281.0 ppm for 6 and 7,
The respectively.
[RuCl2(ϭCϭC[Se(iPr)Ph](PPh3)2] [148.89(6)°].[41]
ClϪRuϪCl angles in the vinylidene complexes [RuCl2-
(ϭCϭCHPh)(PR3)2] [PR3: PCy3
ϭ
158.31(7)°[5b]
/
Preparation of (Aqua)(vinylidene) Complexes
[OsCl2(H2O)(؍C؍CHR)(PPh3)2]
156.93(2)°;[6] PiPr3 ϭ 158.63(4)°[6]] are significantly larger,
however. The OsϪC(1)ϪC(2) unit is nearly linear, with an
OsϪC(1)ϪC(2) angle of 175.5(2)° and OsϪC(1) and
During the process of recording the 31P{1H} NMR spec-
tra of the vinylidene complexes 6 and 7 with commercially
available CD2Cl2, it was found that the chemical shifts of
the signals of the vinylidene complexes changed with differ-
ent batches of solvent and with time when a non-sealed
NMR tube was used. It was suspected that this change
might be caused by coordination of water present in solu-
˚
C(1)ϪC(2) bond lengths of 1.796(3) and 1.320(4) A, respec-
tively, which compare well with those reported for other
(vinylidene)osmium complexes.[8Ϫ16]
˚
Table 2. Selected bond lengths [A] and bond angles [°] for [OsCl2-
(ϭCϭCHCMe3)(PPh3)2] (8)
tion
to
give
the
(aqua)(vinylidene)
complexes
[OsCl2(H2O)(ϭCϭCHR)(PPh3)2], which equilibrate with
[OsCl2(ϭCϭCHR)(PPh3)2]. As a result of fast dissociation
and association of water, only one 31P signal with an aver-
age 31P shift is observed at room temperature. Different
amounts of water present in the solution will therefore af-
fect the relative amounts of the five-coordinate vinylidene
complexes and the corresponding six-coordinate (aqua)(vi-
nylidene) complexes, therefore resulting in different 31P
chemical shifts in the NMR spectra. This speculation was
confirmed by experiments. At low temperature, the 31P{1H}
NMR spectra in commercial CD2Cl2 show two singlets. The
chemical shift of one of the 31P signals is close to that of
[OsCl2(ϭCϭCHAr)(PPh3)2] in freshly dried CD2Cl2. The
other signal can therefore be attributed to [OsCl2(H2O)-
(ϭCϭCHR)(PPh3)2]. Treatment of a blue solution of 6 or
7 in CD2Cl2 in an NMR tube with a drop of water gave an
orange solution immediately, the 31P{1H} NMR spectra of
which shows sharp singlets at δ ഠ Ϫ3.6 or Ϫ3.8 ppm,
respectively. The chemical shifts are very close to those of
the 31P signals suspected for the (aqua)(vinylidene) com-
plexes observed at low temperature. The possibility of isom-
erism arising from the rotation of the vinylidene group at
low temperature can be excluded because such a rotation
does not generate two different electronically favourable
conformers.
Os(1)ϪCl(1)
Os(1)ϪP(1)
Os(1)ϪC(1)
C(2)ϪC(3)
2.3399(7) Os(1)ϪCl(2)
2.3698(7) Os(1)ϪP(2)
1.796(3) C(1)ϪC(2)
1.521(4)
2.3457(6)
2.3690(7)
1.320(4)
P(1)ϪOs(1)ϪP(2) 168.13(2)
C(1)ϪOs(1)ϪCl(1) 103.28(8)
Cl(1)ϪOs(1)ϪP(1) 88.22(2)
Cl(1)ϪOs(1)ϪP(2) 87.27(2)
C(1)ϪOs(1)ϪP(1)
C(2)ϪC(1)ϪOs(1) 175.5(2)
Cl(1)ϪOs(1)ϪCl(2) 149.31(2)
C(1)ϪOs(1)ϪCl(2) 107.39(8)
Cl(2)ϪOs(1)ϪP(1)
Cl(2)ϪOs(1)ϪP(2)
C(1)ϪOs(1)ϪP(2)
C(1)ϪC(2)ϪC(3)
89.69(2)
88.61(2)
95.57(9)
129.1(3)
96.15(9)
As mentioned previously, (vinylidene)osmium complexes
with the general composition [OsCl2(ϭCϭCHR)(PR3)2] are
still very rare. Esteruelas et al. recently reported the vinyl-
idene complex [OsCl2(ϭCϭCHPh)(PiPr3)2], which was pre-
pared by elimination of the imine ligands from the (imine)-
(vinylidene)
complexes
[OsCl2(ϭCϭCHPh)(NHϭ
CR2)(PiPr3)2] [CR2 ϭ CMe2, C(CH2)5] in a refluxing tolu-
ene solution.[13] As far as we know, complex 8 is the first
structurally characterized osmium complex of this kind.
Other reported five-coordinate (vinylidene)osmium com-
plexes include [OsHCl(ϭCϭCHR)(PRЈ3)2] (PRЈ3 ϭ PCy3,
PiPr3],[19,24,37,42] [OsCl(ϭNϭCR2)(ϭCϭCHPh)(PiPr3)2],[13]
[OsCl(ϭCϭCHR)(2,6-[P(tBu)2CH2]2C6H3)],[11]
[Os[C-
(CϵCR)ϭCHR)Cl(ϭCϭCHR)(PPh3)2][22,23] and [Os(CHϭ
CHSiMe3)Cl(ϭCϭCHPh)(PiPr3)2].[43] These compounds
adopt a Y-shaped geometry around the osmium atom.
Consistent with the solid-state structure, a freshly pre-
pared and vacuum-dried sample of 8 in freshly distilled dry
CD2Cl2 at room temperature shows a singlet 31P{1H} signal
at δ ϭ 3.4 ppm. The 1H NMR spectrum in CD2Cl2 exhibits
a triplet at δ ϭ 1.20 ppm with a P-H coupling constant of
3.6 Hz for the vinylidene ϭCH proton and the 13C{1H}
The (aqua)(vinylidene) complexes [OsCl2(H2O)(ϭCϭ
CHPh)(PPh3)2] (9) and [OsCl2(H2O)(ϭCϭCH-p-to-
lyl)(PPh3)2] (10) were isolated as orange solids on a prepara-
tive scale by treatment of 6 and 7 with excess water [Equa-
tion (4)]. Orange solids of 9 and 10 were also obtained when
blue solids of 6 and 7 were exposed to air for 18 h.
NMR spectrum displays two triplets at δ ϭ 274.1 (JP,C
ϭ
12.5 Hz) and 120.5 ppm (JP,C ϭ 5.5 Hz), which are due to
C-α and -β of the vinylidene ligand, respectively.
(4)
Complexes 6 and 7 presumably have similar structures,
as indicated by their NMR spectroscopic data. Freshly pre-
pared and vacuum-dried samples of 6 and 7 in freshly dis-
tilled CD2Cl2 at room temperature show the 31P{1H} sig-
The solid-state structure of 9 (Figure 4) was confirmed
1
nals at δ ϭ 9.6 and 9.2 ppm, respectively. The H NMR by an X-ray diffraction study. Selected bond lengths and
spectra exhibits triplets at δ ϭ 2.56 and 2.46 ppm for the angles are given in Table 3. The geometry around the os-
vinylidene ϭCH protons of 6 and 7, respectively. The mium atom in 9 can be viewed as a distorted octahedron
13C{1H} NMR spectra displays C-α signals of the vinyl- with two PPh3 ligands trans to each other lying in the axial
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[OsCl2(ϭCϭCHR)(PPh3)2] and Related Complexes
FULL PAPER
positions. The equatorial plane is formed by two chloro, the
The water in 9 and 10 is only weakly bound to the metal
vinylidene and water ligands with the coordinated center. Thus, when the orange solids of 9 or 10 are placed
water molecule trans to the vinylidene ligand under vacuum for 3 h, the color changed to blue, indicating
[O(1W)ϪOsϪC(1) ϭ 175.8(2)°]. The two mutually trans- the reformation of 6 or 7. Similarly, if the isolated orange
disposed chloro ligands severely bend away from the vinyl- solids of 9 or 10 are redissolved in CD2Cl2, the 31P{1H}
idene ligand and toward the water molecule with a NMR spectra at room temperature show a broad signal
Cl(1)ϪOsϪCl(2) angle of 158.56(5)° and Cl(1)ϪOsϪO and with a chemical shift significantly downfield from those ob-
Cl(2)ϪOsϪO angles of 81.13(11)° and 77.53(11)°, respec- served in the presence of added water, indicating that water
tively. These angles deviate greatly from the ideal value of is partially dissociated and the equilibrium shown in Equa-
180° for a trans angle and 90° for a cis angle. The vinylidene tion (4) occurs in solution. Thus, the NMR spectroscopic
ligand is bound to the metal atom in a nearly linear fashion data of 9 and 10 have to be collected in the presence of
with an OsϪC(1)ϪC(2) angle of 174.7(6)°. The OsϪC(1) added water. The 13C{1H} NMR spectrum of 9 in a CD2Cl2
[1.812(7) A] and C(1)ϪC(2) [1.298(8) A] bond lengths solution saturated with H2O shows the OsϭC 13C{1H} sig-
˚
˚
1
are similar to those of 8, and compare well with those nal as a triplet at δ ϭ 289.1 ppm (JP,C ϭ 11.4 Hz). The H
observed in other (vinylidene)osmium complexes.[8Ϫ16] NMR signal of ϭCϭCH2 of 9 is observed at δ ϭ 2.48 ppm
The OsϪO bond length is 2.289(4) A, which is close to at room temp. and at δ ϭ 2.61 ppm at 211 K. The 1H NMR
˚
those in [OsCl(ϭCϭCHPh)(NHϭCMe2)(H2O)(PiPr3)2]OTf signal of H2O is observed at δ ϭ 1.95 ppm at 211 K. The
[14]
˚
[2.281(6) A],
[OsCl(ϭCHPh)(H2O)(CO)(PiPr3)2]BF4 NMR spectroscopic data of 9 are consistent with the solid-
[OsMe(H2O)(CO)2(PMe3)2]OTf [2.155(6) state structure. Complex 10 presumably has a structure
[44a]
˚
[2.182(5) A],
[44b]
[44c]
[Cp*Os(η3-C4H7)Me(H2O)]BF4
[2.158(5) A] similar to that of 9, as judged by its spectroscopic data.
˚
˚
A],
and [OsCl2(H2O)(ϵCCHϭCPh2)(PPh3)2]BF4 [2.209(5)
A].
As indicated by NMR experiments, complex 8 also reacts
with water to give the (aqua)(vinylidene) complex
[OsCl2(H2O)(ϭCϭCHCMe3)(PPh3)2] (11). Thus, the
31P{1H} NMR spectrum of a sample of 8 in commercially
available CD2Cl2 at room temperature shows a singlet at
δ ϭ 2.8 ppm which is slightly upfield from that obtained
with dry CD2Cl2. At 188 K, this singlet splits into two
peaks at δ ϭ 3.6 and Ϫ10.2 ppm, which can be attributed
to [OsCl2(ϭCϭCHCMe3)(PPh3)2] (8) and [OsCl2(H2O)-
(ϭCϭCHCMe3)(PPh3)2] (11), respectively. Similarly, the 1H
NMR spectrum in CD2Cl2 at room temperature shows one
CϭCH signal at δ ϭ 1.17 ppm and at 188 K two CϭCH
signals at δ ϭ 1.50 and 0.91 ppm, which can be assigned to
8 and 11, respectively. The water proton signal appears as
a broad peak at δ ϭ 2.12 ppm at room temperature, which
sharpens at low temperature with a similar chemical shift
and gives a relative integration of 2:1 with the less-intense
vinylidene signal of 11. As further evidence for the forma-
tion of 11, addition of a drop of water to a solution of 8 in
[45]
˚
Figure 4. Molecular structure for [OsCl2(H2O)(ϭCϭCHPh)- commercial CD2Cl2 in an NMR tube causes the 31P signal
(PPh3)2] (9)
1
to shift from δ ϭ 2.8 ppm to Ϫ5.8 ppm, and the H signal
of ϭCCH to shift from δ ϭ 1.17 ppm to 0.91 ppm. The
upfield shift of the 31P signal is expected because the rela-
tive amount of 11 is increased when the concentration of
water in the solution is increased. However, the 31P shift
cannot, even in the presence of excess water, reach the value
of δ ϭ Ϫ10.2 ppm observed for 11 at low temperature, sug-
gesting that the equilibrium constant is small (see below).
˚
Table 3. Selected bond lengths [A] and angles [°] for [OsCl2(H2O)-
(ϭCϭCHPh)(PPh3)2]·C6H6 (9·C6H6)
Os(1)ϪP(1)
Os(1)ϪCl(1)
Os(1)ϪC(1)
C(1)ϪC(2)
2.3848(15) Os(1)ϪP(2)
2.3699(15) Os(1)ϪCl(2)
1.812(7) Os(1)ϪO(1 W)
1.298(8) C(2)ϪC(3)
2.3959(15)
2.3886(14)
2.289(4)
1.479(9)
During the process of the NMR study, it was found that
these vinylidene species (8 and 11) are unstable in solution,
especially in the presence of added water. The major de-
composition product is the carbyne complex 4. Other de-
tectable decomposition species include a small amount of
PPh3 and others showing unidentified doublet and triplet
signals. The decomposition is likely initiated by the pro-
tonation of the vinylidene ligand of 11 with water present
in the solution. Owing to the instability and incomplete
P(1)ϪOs(1)ϪP(2)
C(1)ϪOs(1)ϪO(1W) 175.8(2)
C(1)ϪC(2)ϪC(3) 127.2(7)
178.88(5)
Cl(1)ϪOs(1)ϪCl(2) 158.56(5)
C(2)ϪC(1)ϪOs(1) 174.7(6)
O(1W)ϪOs(1)ϪP(1) 91.07(9)
O(1W)ϪOs(1)ϪCl(1) 81.13(11) O(1W)ϪOs(1)ϪCl(2) 77.58(11)
C(1)ϪOs(1)ϪCl(1)
C(1)ϪOs(1)ϪP(1)
Cl(1)ϪOs(1)ϪP(1)
Cl(1)ϪOs(1)ϪP(2)
102.54(18) C(1)ϪOs(1)ϪCl(2)
87.08(16) C(1)ϪOs(1)ϪP(2)
88.84(5)
90.83(6)
98.83(19)
91.96(16)
94.06(6)
86.64(6)
P(1)ϪOs(1)ϪCl(2)
Cl(2)ϪOs(1)ϪP(2)
O(1W)ϪOs(1)ϪP(2) 89.93(10)
Eur. J. Inorg. Chem. 2004, 2837Ϫ2846
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2841

T. B. Wen, W. Y. Hung, Z. Y. Zhou, M. F. Lo, I. D. Williams, G. Jia
FULL PAPER
conversion of 8 to 11, even in the presence of excess water, temperature, the OsϭCϭCH vinylidene proton displays
complex 11 could not be isolated.
only one triplet at δ ϭ 2.54 ppm with a P-H coupling con-
stant of 3.3 Hz. This signal is somewhat broader when the
temperature is lowered and at 190 K gives rise to two broad
singlets (the broadening is probably due to unresolved
coupling with the 31P nuclei) at δ ϭ 2.71 and 2.65 ppm in an
approximate ratio of 5:1. The water proton signal at 190 K
appears as a singlet at δ ϭ 1.88 ppm with a relative inte-
gration of 2:1 with the less-intense vinylidene signal at δ ϭ
2.65 ppm. The water content in the solution affects the ap-
pearance of the variable-temperature spectra. Thus, when a
solution with an Os/H2O molar ratio of 1:1.6 was used in
the variable-temperature experiments, the NMR spectra
show a singlet 31P signal with a chemical shift between
those of 6 and 9 at room temperature, as one might expect,
but only show the signal of the (aqua)(vinylidene) complex
9, while the signal of 6 cannot be detected, when the tem-
perature is lowered below 255 K, due to the higher affinity
of the metal center for H2O at low temperature. The vari-
able-temperature spectra of 7/10 and 8/11 show spectro-
scopic features similar to those of 6 and 8.
NMR Study of the Equilibria
We carried out variable-temperature 31P{1H} and 1H
NMR experiments to study the dynamic process between
[OsCl2(ϭCϭCHR)(PPh3)2]
and
[OsCl2(H2O)(ϭCϭ
CHR)(PPh3)2]. As an illustration, the 31P{1H} NMR spec-
tra of a sample of 6 in wet CD2Cl2 (the Os/H2O molar ratio
in solution is 1:0.2) at different temperatures are shown in
Figure 5. At room temperature (298 K), the 31P signal is a
singlet at δ ϭ 9.1 ppm, which broadens and shifts upfield
upon decreasing the temperature to 239 K. The upfield shift
of the 31P signal on lowering the temperature indicates that
the equilibrium is shifted toward the formation of the
(aqua)(vinylidene) complex 9 at lower temperature. The sin-
glet separates into two peaks with unequal intensities when
the temperature is lowered below 217 K. At 198 K, two
sharp singlets in about a 5:1 ratio at δ ϭ 11.6 and Ϫ3.4 ppm
are observed, due to the 31P signals of 6 and 9, respectively.
Similarly, in the 1H NMR spectrum in CD2Cl2 at room
The equilibrium constants at several temperatures (be-
tween 298 and 270 K) were estimated on the basis of vari-
1
able-temperature 31P{1H} and H NMR measurements of
samples of 9, 10 and 11 in CD2Cl2. The relative amounts
of the five-coordinate vinylidene complexes and their corre-
sponding (aqua)(vinylidene) complexes were calculated
from the average 31P chemical shifts assuming that the
chemical shifts of five-coordinate vinylidene complexes and
their corresponding (aqua)(vinylidene) complexes do not
change with temperature.[46] The relative concentrations of
coordinated and free water in the solution can be obtained
from the integrals of the H2O signals in the 1H NMR spec-
tra and the concentrations of the aqua complexes. The equi-
librium constants at different temperatures calculated based
Figure 5. The variable-temperature 31P{1H} NMR spectra of
[OsCl2(ϭCϭCHPh)(PPh3)2]
(6)
and
[OsCl2(H2O)(ϭCϭ
CHPh)(PPh3)2] (9) in wet CD2Cl2 (Os/H2O molar ratio in solu-
tion ϭ 1:0.2) at 121.5 MHz
Table 4. Parameters for the equilibria between [OsCl2(ϭCϭCHR)(PPh3)2] and [OsCl2(H2O)(ϭCϭCHR)(PPh3)2]
Ǟ
ǟ
[OsCl2(ϭCϭCHPh)(PPh3)2] ϩ H2O [OsCl2(H2O)(ϭCϭCHPh)(PPh3)2] (9)
T [K]
298
202.7
292
312.6
282
788.9
270
3085
K[a]
lnK
5.312
Ϫ3.15
5.745
Ϫ3.33
6.671
Ϫ3.73
8.034
Ϫ4.30
∆G0 [kcal·molϪ1
]
Ǟ
ǟ
[OsCl2{ϭCϭCH(p-tolyl)}(PPh3)2] ϩ H2O [OsCl2(H2O){ϭCϭCH(p-tolyl)}(PPh3)2] (10)
T [K]
298
172.1
5.148
Ϫ3.05
287
506.9
6.228
Ϫ3.55
280
1197
7.087
Ϫ3.94
270
K[b]
4684
8.452
Ϫ4.53
lnK
∆G0 [kcal·molϪ1
]
Ǟ
ǟ
[OsCl2(ϭCϭCHCMe3)(PPh3)2] ϩ H2O [OsCl2(H2O)(ϭCϭCHMe3)(PPh3)2] (11)
T (K)
298
15.51
2.741
290
35.22
3.562
285
69.37
4.239
279
275
416.4
6.032
Ϫ3.30
K[c]
172.8
5.152
Ϫ2.86
lnK
∆G0 [kcal·molϪ1
]
Ϫ1.62
Ϫ2.05
Ϫ 2.40
[a]
[b]
The values were obtained with a CD2Cl2 solution having an Os/H2O molar ratio of 1:1.6. The values were obtained with a CD2Cl2
solution having an Os/H2O molar ratio of 1:1. [c] The values were obtained with a CD2Cl2 solution having an Os/H2O molar ratio of 1:0.4.
2842
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 2837Ϫ2846

[OsCl2(ϭCϭCHR)(PPh3)2] and Related Complexes
FULL PAPER
(400 MHz). 1H and 13C NMR chemical shifts are relative to TMS,
on these data are summarized in Table 4. A plot of lnK
against reciprocal absolute temperature gave a straight line.
According to the equation lnK ϭ Ϫ(∆H0/R)(1/T) ϩ ∆S0/R,
the standard enthalpy and the standard entropy change of
the reaction can be calculated from the slope of the straight
line and the intercept, respectively. Approximate values of
and 31P NMR chemical shifts are relative to 85% H3PO4.
[OsCl3(ϵC؊CH2Ph)(PPh3)2] (2): HCl·OEt2 (1.00 mL,1.0  in di-
ethyl ether solution, 1.0 mmol) and HCϵCPh (0.32 mL, 2.9 mmol)
were added to a solution of [OsCl2(PPh3)3] (0.50 g, 0.48 mmol) in
benzene (15 mL). The reaction mixture was stirred at room tem-
∆H0 ϭ Ϫ22.7 kcal·molϪ1 and ∆S0 ϭ Ϫ70.96 cal·molϪ1·KϪ1 perature for 6 h to give a yellow microcrystalline solid, which was
collected by filtration, washed with diethyl ether (2 ϫ 20 mL) and
dried under vacuum (0.33 g). The filtrate was concentrated to ca.
5 mL, and addition of diethyl ether (20 mL) to the residue pro-
duced additional yellow solid, which was collected by filtration,
washed with diethyl ether (2 ϫ 20 mL), and dried under vacuum
overnight (0.05 g). Total yield: 0.38 g (86%). 1H NMR
(399.65 MHz, CDCl3): δ ϭ 1.77 (s, 2 H, OsϵCCH2), 6.46 (d,
were calculated for the equilibrium between 8 and 11 in
CD2Cl2, and the value of ∆G0 at 298 K was Ϫ1.62
kcal·molϪ1. For the equilibrium between 6 and 9 in
CD2Cl2, the relevant values were calculated to be ∆H0 ϭ
Ϫ15.7 kcal·molϪ1, ∆S0 ϭ Ϫ42.3 cal·molϪ1·KϪ1 and
∆G0
ϭ Ϫ3.15 kcal·molϪ1. These results indicate that
(298)
formation of the (aqua)(vinylidene) is exothermic and that
the equilibria are shifted to the (aqua)(vinylidene) com-
plexes when the temperature is lowered, as mentioned pre-
viously.
As can be seen from Table 4, the equilibrium constant at
room temperature for 6/9 is similar to that of 7/11 and is
about 13 times as large as that of 8/11, indicating that
[OsCl2(ϭCϭCHAr)(PPh3)2] (6 and 7) have a higher affinity
for H2O than [OsCl2(ϭCϭCHCMe3)(PPh3)2] (8). This dif-
ference may be related to that fact that CMe3 is more elec-
JH,H ϭ 7.1 Hz, 2 H, o-C6H5), 7.08 (t, JH,H ϭ 7.6 Hz, 2 H, m-C6H5),
7.19 (t, JH,H ϭ 7.6 Hz, 1 H, p-C6H5), 7.29Ϫ7.38 (m, 18 H, PPh3),
7.81Ϫ7.86 (m, 12 H, PPh3) ppm. 13C{1H} NMR (100.4 MHz,
CD2Cl2): δ ϭ 278.2 (t, JP,C ϭ 11.1 Hz, OsϵC), 134.9Ϫ125.0 (m,
C6H5, PPh3), 57.3 (s, OsϵCCH2) ppm. 31P{1H} NMR (121.5 MHz,
CDCl3): δ ϭ Ϫ12.9 (s) ppm. C44H37Cl3OsP2 (924.3): calcd. C 57.18,
H 4.04; found C 57.35, H 4.19.
[OsCl3{ϵC؊CH2(p-tolyl)}(PPh3)2] (3): HCl·OEt2 (1.00 mL, 1.0 
in diethyl ether solution, 1.0 mmol) and 4-ethynyltoluene (0.24 mL,
1.9 mmol) were added to a solution of [OsCl2(PPh3)3] (0.50 g,
tron-donating than Ar, thus the Lewis acidities of 6 and 7 0.48 mmol) in benzene (15 mL). The reaction mixture was stirred
at room temperature for 6 h to give a yellow microcrystalline solid,
which was collected by filtration, washed with diethyl ether (2 ϫ
20 mL) and dried under vacuum (0.32 g). The filtrate was concen-
trated to about 5 mL, and addition of diethyl ether (20 mL) to the
residue produced additional yellow solid, which was collected by
filtration, washed with diethyl ether (2 ϫ 15 mL), and dried under
vacuum overnight (31 mg). Total yield: 0.35 g (78%). 1H NMR
(399.65 MHz, CDCl3): δ ϭ 1.72 (s, 2 H, OsϵCCH2), 2.22 (s, 3 H,
are higher than that of 8.
Conclusions
Reaction of [OsCl2(PPh3)3] with terminal acetylenes
HCϵCR (R ϭ Ph, p-tolyl, CMe3) in the presence of HCl
readily
produced
the
carbyne
complexes
C6H4CH3), 6.21 (d, JH,H ϭ 8.0 Hz, 2 H, C6H4) 6.79 (d, JH,H
8.0 Hz, 2 H, C6H4), 7.30 (m, 18 H, PPh3), 7.80 (m, 12 H, PPh3)
ppm. 13C{1H} NMR (100.4 MHz, CD2Cl2): δ ϭ 280.1 (t, JP,C
ϭ
[OsCl3(ϵCCH2R)(PPh3)2]. Due to the acidic nature of the
protons α to the carbyne carbon atom, the vinylidene com-
ϭ
plexes [OsCl2(ϭCϭCHR)(PPh3)2] (R ϭ CMe3, Ph, p-tolyl) 12.0 Hz, OsϵC), 138.0Ϫ122.1 (m, C6H5, PPh3), 57.1 (s,
OsϵCCH2), 21.2 (s, C6H4-CH3) ppm. 31P{1H} NMR (121.5 MHz,
CDCl3): δ ϭ Ϫ12.1 (s) ppm. C45H39Cl3OsP2 (938.3): calcd. C 57.60,
H 4.19; found C 57.40, H 4.34.
can be easily prepared from these carbyne complexes by
treatment with NEt3. Interestingly, these vinylidene com-
plexes are hygroscopic and react with water to give
[OsCl2(H2O)(ϭCϭCHR)(PPh3)2] reversibly.
NMR studies show that the vinylidene complexes [OsCl2(ϭ
CϭCHR)(PPh3)2] (R ϭ Ph, p-tolyl) have a higher tendency
Dynamic
[OsCl3(ϵCCH2CMe3)(PPh3)2] (4): HCϵCCMe3 (0.28 mL,
2.3 mmol) and HCl·OEt2 (0.80 mL, 0.80 mmol, 1.0  in diethyl
ether solution) were added to a solution of [OsCl2(PPh3)3] (0.40 g,
to form the aqua complexes than does [OsCl2(ϭCϭ 0.38 mmol) in benzene (15 mL). The reaction mixture was stirred
at room temperature for 6 h to give a yellow microcrystalline solid,
which was collected by filtration, washed with diethyl ether (2 ϫ
20 mL) and dried under vacuum (0.20 g). The filtrate was concen-
trated to ca. 3 mL, and addition of diethyl ether (20 mL) to the
residue produced additional yellow solid, which was collected by
filtration, washed with diethyl ether (2 ϫ 20 mL), and dried under
vacuum overnight (0.08 g). Total yield: 0.28 g (82%). The spectro-
scopic data have been reported previously.[22]
CHCMe3)(PPh3)2]. Thus, the (aqua)(vinylidene) complexes
[OsCl2(ϭCϭCHR)(H2O)(PPh3)2] (R ϭ Ph, p-tolyl) could
be isolated by treatment of the anhydrous vinylidene com-
plexes with water.
Experimental Section
General: All manipulations were carried out at room temperature
under nitrogen using standard Schlenk techniques, unless otherwise
stated. Solvents were distilled under nitrogen from sodium/benzo-
phenone (hexane, diethyl ether, THF, benzene) or calcium hydride
(dichloromethane, CHCl3). The starting material [OsCl2(PPh3)3][47]
was prepared according to literature methods. Microanalyses were
[OsCl3(ϵCCH3)(PPh3)2] (5): HCϵCSiMe3 (0.27 mL, 1.9 mmol)
and HCl·OEt2 (1.20 mL, 1.0  in diethyl ether solution, 1.2 mmol)
were added to a solution of [OsCl2(PPh3)3] (0.50 g, 0.48 mmol) in
benzene (15 mL). The reaction mixture was stirred at room tem-
perature for 8 h to give a yellow microcrystalline solid, which was
collected by filtration, washed with diethyl ether (2 ϫ 20 mL) and
performed by M-H-W Laboratories (Phoenix, AZ). 1H, 13C{1H} dried under vacuum (0.25 g). The filtrate was concentrated to ca.
and 31P{1H} NMR spectra were collected with a Bruker ARX-300
3 mL, and addition of diethyl ether (20 mL) to the residue pro-
duced additional yellow solid, which was collected by filtration,
spectrometer (300 MHz) or
a
JOEL EX-400 spectrometer
Eur. J. Inorg. Chem. 2004, 2837Ϫ2846
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T. B. Wen, W. Y. Hung, Z. Y. Zhou, M. F. Lo, I. D. Williams, G. Jia
FULL PAPER
washed with diethyl ether (2 ϫ 15 mL), and dried under vacuum
overnight (0.04 g). Total yield: 0.29 g (71%). 1H NMR
(300.13 MHz, CD2Cl2): δ ϭ 0.04 (t, JP,H ϭ 2.5 Hz, 3 H, CH3),
PPh3), 7.66Ϫ7.71 (m, 12 H, PPh3) ppm. The signal of H2O appears
at room temp. at δ ϭ 1.73 ppm and at 211 K at δ ϭ 1.86 ppm with
an integral of 2:1 relative to that of the vinylidene signal. 13C{1H}
7.36Ϫ7.43 (m, 18 H, PPh3), 7.89Ϫ7.96 (m, 12 H, PPh3) ppm. NMR (100.40 MHz, freshly distilled CD2Cl2): δ ϭ 274.1 (t, JP,C
13C{1H} NMR (100.40 MHz, CD2Cl2): δ ϭ 283.7 (t, JP,C
12.5 Hz, OsϭC), 134.9Ϫ128.4 (m, PPh3), 120.5 (t, JP,C ϭ 5.5 Hz,
12.3 Hz, OsϵC), 135.1Ϫ127.9 (m, PPh3), 36.9 (s, OsϵC-CH3) ppm. OsϭCϭCH), 32.60 [s, C(CH3)3], 27.47 [s, C(CH3)3] ppm. 31P{1H}
31P{1H} NMR (121.5 MHz, CD2Cl2):
Ϫ13.5 (s) ppm. NMR (121.5 MHz, freshly distilled CD2Cl2): δ ϭ 3.4 (s) ppm. FAB-
C38H33Cl3OsP2 (848.2): calcd. C 53.81, H 3.92; found C 53.60, H MS (NBA): m/z ϭ 868 [Mϩ]. C42H40Cl2OsP2 (867.8): calcd. C
ϭ
ϭ
δ
ϭ
4.18.
58.13, H 4.65; found C 58.49, H 4.53.
[OsCl2(؍C؍CHPh)(PPh3)2] (6): NEt3 (0.43 mL, 3.1 mmol) was
added to a CH2Cl2 (40 mL) solution of [OsCl3(ϵCCH2Ph)(PPh3)2]
(0.57 g, 0.62 mmol). The reaction mixture rapidly changed color
from yellow to blue. After stirring for 1 h, the solvent was removed
completely under vacuum and the resulting blue solid was extracted
with benzene (30 mL). The extract was filtered through Celite to
remove the insoluble Et3N·HCl. The filtrate was concentrated to
ca. 1 mL and diethyl ether was slowly added to give a blue solid,
which was collected by filtration, washed with diethyl ether (2 ϫ
10 mL) and dried under vacuum overnight. Yield: 0.47 g (85%). 1H
[OsCl2(H2O)(؍C؍CHPh)(PPh3)2] (9): Water (0.2 mL) was added
to
a blue solution of [OsCl2(ϭCϭCHPh)(PPh3)2] (0.15 g,
0.17 mmol) in CH2Cl2 (10 mL). The solution turned orange im-
mediately. After stirring for 20 min, the solvent was pumped off to
give an orange paste. Diethyl ether (10 mL) was added to the resi-
due to give an orange solid, which was collected by filtration,
washed with diethyl ether (2 ϫ 5 mL) and dried under vacuum for
30 min. Yield: 0.14 g (91%). 1H NMR (300.13 MHz, CD2Cl2): δ ϭ
2.48 (t, JP,H ϭ 3.3 Hz, 1 H, OsϭCϭCH), 6.70 (d, JH,H ϭ 7.2 Hz,
2 H, o-C6H5), 6.76 (t, JH,H ϭ 7.4 Hz, 1 H, p-C6H5), 7.08 (t, JH,H ϭ
7.4 Hz, 2 H, m-C6H5), 7.28Ϫ7.40 (m, 18 H, PPh3), 7.70Ϫ7.76 (m,
12 H, PPh3) ppm. The signal of H2O appears at room temp. at δ ϭ
1.77 ppm and at 211 K at δ ϭ 1.95 ppm with an integral of 2:1
relative to that of the vinylidene ϭCH signal. 13C{1H} NMR
(100.4 MHz, CD2Cl2): δ ϭ 289.1 (t, JP,C ϭ 11.4 Hz, OsϭC),
134.7Ϫ123.8 (m, C6H5, PPh3), 112.3 (t, JP,C ϭ 4.4 Hz, OsϭCϭCH)
ppm. 31P{1H} NMR (121.5 MHz, CD2Cl2 in the presence of a drop
of water): δ ϭ Ϫ3.6 (s) ppm. C44H38Cl2OOsP2 (905.8): calcd. C
58.34, H 4.23; found C 58.54, H 4.42.
NMR (300.13 MHz, freshly distilled CD2Cl2): δ ϭ 2.56 (t, JP,H
ϭ
3.3 Hz, 1 H, OsϭCϭCH), 6.48 (d, JH,H ϭ 7.4 Hz, 2 H, o-C6H5),
6.71 (t, JH,H ϭ 7.4 Hz, 1 H, p-C6H5), 7.02 (t, JH,H ϭ 7.4 Hz, 2 H,
m-C6H5), 7.25Ϫ7.41 (m, 18 H, PPh3), 7.57Ϫ7.64 (m, 12 H, PPh3)
ppm. 13C{1H} NMR (100.4 MHz, freshly distilled CD2Cl2): δ ϭ
280.8 (br., OsϭC), 135.0Ϫ124.3 (m, C6H5, PPh3), 112.1 (t, JP,C
ϭ
4.8 Hz, OsϭCϭCH) ppm. 31P{1H} NMR (121.5 MHz, freshly dis-
tilled CD2Cl2): δ ϭ 9.6 (s) ppm. C44H36Cl2OsP2 (887.8): calcd. C
59.53, H 4.09; found C 59.54, H 4.01.
[OsCl2{؍C؍CH(p-tolyl)}(PPh3)2] (7): NEt3 (0.44 mL, 3.2 mmol)
was added to a CH2Cl2 (40 mL) solution of [OsCl3{ϵCCH2(p-
tolyl)}(PPh3)2] (0.50 g, 0.53 mmol). The reaction mixture rapidly
changed color from yellow to blue. After stirring for 1 h, the solvent
was removed completely under vacuum and the resulting blue solid
was extracted with benzene (30 mL). The extract was filtered
through Celite to remove the insoluble Et3N·HCl. The filtrate was
concentrated to ca. 1 mL and diethyl ether was slowly added to
give a blue solid, which was collected by filtration, washed with
diethyl ether (2 ϫ 10 mL) and dried under vacuum overnight.
[OsCl2(H2O){؍C؍CH(p-tolyl)}(PPh3)2] (10): Water (0.2 mL) was
added to a blue solution of [OsCl2{ϭCϭCH(p-tolyl)}(PPh3)2]
(0.15 g, 0.17 mmol) in CH2Cl2 (10 mL). The solution turned orange
immediately. After stirring for 20 min, the solvent was pumped off
to give an orange paste. Diethyl ether (10 mL) was added to the
residue to give an orange solid, which was collected by filtration,
washed with diethyl ether (2 ϫ 5 mL) and dried under vacuum for
30 min. Yield: 0.14 g (89%). 1H NMR (300.13 MHz, CD2Cl2): δ ϭ
2.38 (s, 3 H, C6H4CH3), 2.42 (t, JP,H ϭ 3.5 Hz, 1 H, OsϭCϭCH),
6.62 (d, JH,H ϭ 8.0 Hz, 2 H, C6H4), 6.92 (d, JH,H ϭ 8.0 Hz, 2 H,
C6H4), 7.30Ϫ7.37 (m, 18 H, PPh3), 7.70Ϫ7.73 (m, 12 H, PPh3)
ppm. The signal of H2O appears at room temp. at δ ϭ 1.73 ppm
and at 190 K at δ ϭ 1.86 ppm with an integral of 2:1 relative to
that of the vinylidene ϭCH signal. 13C{1H} NMR (100.4 MHz,
CD2Cl2): δ ϭ 293.7 (t, JP,C ϭ 14.1 Hz, OsϭC), 135.1Ϫ125.4 (m,
C6H4, PPh3), 112.5 (t, JP,C ϭ 4.5 Hz, OsϭCϭCH), 20.8 (s, C6H4-
CH3) ppm. 31P{1H} NMR (121.5 MHz, CD2Cl2): δ ϭ Ϫ3.8 (s)
ppm. C45H40Cl2P2OOs (919.9): calcd. C 58.76, H 4.38; found C
58.63, H 4.12.
1
Yield: 0.42 g (88%). H NMR (300.13 MHz, CD2Cl2): δ ϭ 2.39 (s,
3 H, C6H4CH3), 2.46 (t, JP,H ϭ 3.4 Hz, 1 H, OsϭCϭCH), 6.40 (d,
JH,H ϭ 8.0 Hz, 2 H, C6H4), 6.87 (d, JH,H ϭ 8.0 Hz, 2 H, C6H4),
7.33Ϫ7.41 (m, 18 H, PPh3), 7.59Ϫ7.62 (m, 12 H, PPh3) ppm.
13C{1H} NMR (100.4 MHz, freshly distilled CD2Cl2): δ ϭ 281.0
(br., OsϭC), 135.0Ϫ124.9 (m, C6H4, PPh3), 112.0 (t, JP,C ϭ 4.5 Hz,
OsϭCϭCH), 20.9 (s, C6H4-CH3) ppm. 31P{1H} NMR
(121.5 MHz, freshly distilled CD2Cl2):
δ ϭ 9.2 (s) ppm.
C45H38Cl2OsP2 (901.8): calcd. C 59.93, H 4.25; found C 59.76, H
4.26.
Observation of 11: Owing to the instability and incomplete conver-
sion of 8 to 11, 11 could not be isolated but could be detected when
a solution of 8 in commercially available CD2Cl2 was monitored
by variable-temperature 31P{1H} and 1H NMR experiments.
Characterization data of 11: 1H NMR (300.13 MHz, CD2Cl2,
188 K): δ ϭ 0.91 (br. s, 1 H, OsϭCϭCH), 2.38 (br., 2 H, H2O)
ppm. 31P{1H} NMR (121.5 MHz, CD2Cl2, 188 K): δ ϭ Ϫ10.2 (br.
s) ppm.
[OsCl2(؍C؍CHCMe3)(PPh3)2] (8): NEt3 (0.31 mL, 1.7 mmol) was
added with stirring to a solution of [OsCl3(ϵCCH2CMe3)(PPh3)2]
(0.50 g, 0.55 mmol) in CH2Cl2 (50 mL). The reaction solution
changed color from orange to brown immediately. The reaction
mixture was stirred at room temperature for 1 h and the solvent
was removed completely under vacuum. The brown solid was ex-
tracted with benzene (15 mL) and the extract filtered through Celite
to remove the insoluble Et3N·HCl. The volume of the brown fil-
trate was reduced to ca. 1 mL. Addition of diethyl ether (20 mL) Crystal-Structure Analyses: Crystals suitable for X-ray diffraction
to the residue produced a purple solid, which was collected by fil- were grown by layering hexane on CH2Cl2 solutions of 2, 5 and 8,
tration, washed with diethyl ether (2 ϫ 10 mL) and hexane (20 mL) or cooling a warm solution of 9 in benzene. Data collection was
1
and dried under vacuum overnight. Yield: 0.29 g (61%). H NMR
(300.13 MHz, freshly distilled CD2Cl2): δ ϭ 0.54 [s, 9 H, C(CH3)3],
1.20 (t, JP,H ϭ 3.6 Hz, 1 H, OsϭCϭCH), 7.42Ϫ7.51 (m, 18 H,
performed with a Bruker Apex CCD Area Detector for 2 and 8
and with a Bruker SMART CCD Area Detector for 5 and 9, using
graphite-monochromated Mo-Kα radiation (λ ϭ 0.71073 A) in all
˚
2844
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2837Ϫ2846

[OsCl2(ϭCϭCHR)(PPh3)2] and Related Complexes
FULL PAPER
Table 5. Crystallographic details for [OsCl3(ϵCCH2Ph)(PPh3)2]·1.5C6H6 (2·1.5C6H6), [OsCl3(ϵCCH3)(PPh3)2]·CH2Cl2 (5·CH2Cl2),
[OsCl2(ϭCϭCHCMe3)(PPh3)2] (8) and [OsCl2(H2O)(ϭCϭCHPh)(PPh3)2]·C6H6 (9·C6H6)
Compound
2·1.5C6H6
5·CH2Cl2
8
9·C6H6
Empirical formula
Formula mass
Temperature [K]
Radiation (Mo-Kα) [A]
Crystal system
C44H37Cl3OsP2·1.5C6H6 C38H33Cl3OsP2·CH2Cl2 C42H40Cl2OsP2
C44H38Cl2OOs P2·C6H6
983.89
293(2)
0.71073
monoclinic
P21/n
16.106(2)
12.3804(14)
21.477(3)
90
96.382(3)
90
4255.9(9)
4
1.536
1041.39
100(2)
933.06
293(2)
867.78
180(2)
˚
0.71073
triclinic
0.71073
triclinic
0.71073
monoclinic
P21/c
¯
¯
Space group
P1 (no. 2)
P1 (no. 2)
˚
a [A]
9.9952(7)
13.9065(10)
17.7242(12)
110.6600(10)
97.6520(10)
98.292(2)
2235.6(3)
2
10.6256(9)
12.9185(12)
14.0763(12)
78.341(2)
89.708(2)
81.302(2)
1869.9(3)
2
22.2749(10)
9.5252(4)
18.7580(8)
90
113.2070(10)
90°
3657.9(3)
4
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
dcalcd. [g·cmϪ3
]
1.547
1.657
1.576
Abs. coeff. [mmϪ1
F(000)
]
3.139
1042
3.880
920
3.749
1728
3.234
1968
Crystal size [mm]
θ range [°]
0.36 ϫ 0.10 ϫ 0.08
1.60 to 27.88
19208
0.36 ϫ 0.32 ϫ 0.25
1.94 to 27.53
12564
8431 (Rint ϭ 0.0353)
7060
0.32 ϫ 0.25 ϫ 0.25
2.36 to 28.31°
21881
8561 (Rint ϭ 0.0260) 9785 (Rint ϭ 0.0849)
7617
0.32 ϫ 0.32 ϫ 0.10
1.90 to 27.57
27413
No. of reflns. collected
No. of indep. reflns.
10057 (Rint ϭ 0.0318)
No. of obsd. reflns. [I Ͼ 2σ(I)] 8921
4759
Absorption correction
Data/restraints/params
Goodness-of-fit on F2
Final Rint [I Ͼ 2σ(I)]
SADABS
10057/0/532
0.992
R1 ϭ 0.0303,
wR2 ϭ 0.0696
1.798/Ϫ0.974
SADABS
8431/3/434
0.989
R1 ϭ 0.0428,
wR2 ϭ 0.1021
2.236/Ϫ0.950
SADABS
8561/0/428
1.037
R1 ϭ 0.0261,
wR2 ϭ 0.0583
1.639/Ϫ0.519
SADABS
9785/0/506
0.764
R1 ϭ 0.0425,
wR2 ϭ 0.0637
1.312/Ϫ0.799
Ϫ3
˚
Largest peak/hole (e·A
)
[2e]
cases. Empirical absorption corrections (SADABS)[48] were applied.
All structures were solved by direct methods, expanded by differ-
ence Fourier syntheses and refined by full-matrix least-squares on
F2 using the Bruker SHELXTL (Version 5.10)[49] program package.
All non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were introduced at their geometric positions and refined as
riding atoms. Further details on crystal data, data collection and
refinements are summarized in Table 5. CCDC-227451
(2·1.5C6H6), -227452 (5·CH2Cl2), -227453 (8) and -227454 (9·C6H6)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/
conts/retrieving.html [or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
ϩ 44-1223-336033; E-mail: deposit@ccdc.cam.ac.uk].
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Published Online May 13, 2004
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