Vinylidene, Allenylidene, and Carbyne Complexes from the Reactions of [OsCl2(PPh3)3] with HC≡CC(OH)Ph 2

Article abstract of DOI:10.1021/om034082m

Treatment of [OsCl₂(PPh₃)₃] with HC≡CC(OH)Ph₂ in benzene at room temperature produces [(PPh ₃)₂C1Os(μ-Cl)₃Os(=C=CHC(OH)Ph ₂)(PPh₃)₂], fac-[OsCl <

Full text of DOI:10.1021/om034082m

Organometallics 2003, 22, 5217-5225
5217
Vin ylid en e, Allen ylid en e, a n d Ca r byn e Com p lexes fr om
th e Rea ction s of [OsCl2(P P h 3)3] w ith HCtCC(OH)P h 2
Ting Bin Wen,† Zhong Yuan Zhou,‡ Man Fung Lo,† Ian D. Williams,† and
Guochen J ia*,†
Department of Chemistry, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon, Hong Kong, and Department of Applied Biology and
Chemical Technology, Hong Kong Polytechnic University, Kowloon, Hong Kong
Received August 2, 2003
Treatment of [OsCl2(PPh3)3] with HCtCC(OH)Ph2 in benzene at room temperature
produces [(PPh3)2ClOs(µ-Cl)3Os(dCdCHC(OH)Ph2)(PPh3)2], fac-[OsCl3(tC-CHdCPh2)-
(PPh3)2], mer-[OsCl3(tC-CHdCPh2)(PPh3)2], and [OsCl2(dCdCdCPh2)(CO)(PPh3)2]. The
latter two complexes are the major products when the reaction is carried out in refluxing
toluene. Treatment of [OsCl2(PPh3)3] with HCtCC(OH)Ph2 in the presence of HCl produces
fac-[OsCl3(tC-CHdCPh2)(PPh3)2] and mer-[OsCl3(tC-CHdCPh2)(PPh3)2]. Treatment of
[OsCl2(PPh3)3] with HCtCC(OH)Ph2 in the presence of HPPh3BF4 produces [OsCl2(tC-
CHdCPh2)(H2O)(PPh3)2]BF4. The structures of all the new complexes have been confirmed
by X-ray diffraction.
In tr od u ction
We have studied the reactions of [OsCl2(PPh3)3] with
terminal acetylenes, to see if related osmium vinylidene
or allenylidene complexes can be similarly obtained. We
have previously reported the reactions of [OsCl2(PPh3)3]
with HCtCR (R ) t-Bu, SiMe3).7,8 It was shown that
the expected osmium vinylidene complexes could not be
isolated from the reactions. Instead, we have isolated
carbyne complexes [OsCl3(tCCH2R)(PPh3)2], osmaben-
zyne complexes, and vinyl-vinylidene complexes [OsX-
(C(CtCR)dCHR)(dCdCHR)(PPh3)2] (X ) Cl, CtCR)
from the reactions. The purpose of this paper is to report
the reaction of [OsCl2(PPh3)3] with HCtCC(OH)Ph2.
During the course of the study, it was briefly reported
that the allenylidene complex [OsCl2(dCdCdCPh2)-
(PPh3)2] can be isolated in 98% yield from the reaction
of [OsCl2(PPh3)3] with HCtCC(OH)Ph2.3 In our study,
however, the allenylidene complex could not be ob-
tained. Rather, we have isolated several new osmium
complexes including the dinuclear complex [(PPh3)2-
ClOs(µ-Cl)3Os(dCdCHC(OH)Ph2)(PPh3)2], trichloro-
vinylcarbyne complexes fac-[OsCl3(tC-CHdCPh2)-
(PPh3)2] and mer-[OsCl3(tC-CHdCPh2)(PPh3)2], and
the carbonyl allenylidene complex [OsCl2(dCdCdCPh2)-
(CO)(PPh3)2]. It is noted that well-characterized osmium
allenylidene complexes are still rare. Reported osmium
allenylidene complexes include [(η5-C9H7)Os(dCdCd
CR2)(PPh3)2]PF6 (R2 ) Ph2, C12H8),9 [CpOsCl(dCdCd
CPh2)(P(i-Pr)3)],10 [CpOs(dCdCdCR2)(P(i-Pr)3)2]PF6,11
Reactions of [RuCl2(PPh3)3] and related compounds
with HCtCR or HCtCC(OH)RR′ have been studied by
several groups.1-5 These reactions usually lead to the
formation of vinylidene or allenylidene complexes. For
example, treatment of [RuCl2(PPh3)3] with HCtCCMe3
produces [RuCl2(dCdCHCMe3)(PPh3)2];1 reaction of
[RuCl2(PPh3)3] with HCtCC(OH)Ph2 in the presence of
NaPF6 in dichloromethane gives the bimetallic complex
[Ru2(µ-Cl)3(dCdCdCPh2)2(PPh3)4]PF6.2 In refluxing THF,
[RuCl2(PPh3)3] reacts with HCtCC(OH)Ph2 to give the
3-phenyl-1-indenylidene complex [RuCl2(C9H5Ph)(PPh3)2]
via the allenylidene intermediate [RuCl2(dCdCdCPh2)-
(PPh3)2].3,4 Reaction of [RuCl2(PPh3)3] with HCtCC-
(OH)Ph2 in the presence of PCy3 in refluxing THF gives
the allenylidene complex [RuCl2(dCdCdCPh2)(PCy3)2].4
These vinylidene or allenylidene complexes are interest-
ing because they are catalytically active for olefin
metathesis.6
† The Hong Kong University of Science and Technology.
‡ Hong Kong Polytechnic University.
(1) (a) Wakatsuki, Y.; Yamazaki, H.; Kumegawa, N.; Satoh, T.;
Satoh, J . Y. J . Am. Chem. Soc. 1991, 113, 9604. (b) Wakatsuki, Y.;
Koga, N.; Yamazaki, H.; Morokuma, K. J . Am. Chem. Soc. 1994, 116,
8105.
(2) Touchard, D.; Guesmi, S.; Bouchaib, M.; Haquette, P.; Daridor,
A.; Dixneuf, P. H. Organometallics 1996, 15, 2579.
(3) Harlow, K. J .; Hill, A. F.; Wilton-Ely, J . D. E. J . Chem. Soc.,
Dalton Trans. 1999, 285.
(4) (a) Schanz, H. J .; J afarpour, L.; Stevens, E. D.; Nolan, S. P.
Organometallics 1999, 18, 5187. (b) Fu¨rstner, A.; Guth, O.; Du¨ffels,
A.; Seidel, G.; Liebl, M.; Gabor, B.; Mynott, R. Chem. Eur. J . 2001, 7,
4811.
(5) For preparation of vinylidene and allenylidene complexes from
complexes related to [RuCl2(PPh3)3], see for example: (a) Gru¨nwald,
C.; Gevert, O.; Wolf, J .; Gonza´lez-Herrero, P.; Werner, H. Organome-
tallics 1996, 15, 1960. (b) Wolf, J .; Stu¨er, W.; Gru¨nwald, C.; Gevert,
O.; Laubender, M.; Werner, H. Eur. J . Inorg. Chem. 1998, 1827. (c)
Wolf, J .; Stu¨er, W.; Gru¨nwald, C.; Werner, H, Schwab, P.; Schulz, M.
Angew. Chem., Int. Ed. 1998, 37, 1124. (d) Katayama, H.; Ozawa, F.
Organometallics 1998, 17, 5190. (e) Saoud, M.; Romerosa, A.; Peruzzini,
M. Organometallics 2000, 19, 4005.
(6) (a) Schwab, P.; Grubbs, R. H.; Ziller, J . W. J . Am. Chem. Soc.
1996, 118, 100. (b) Katayama, H.; Ozawa, F. Chem. Lett. 1998, 67. (c)
Katayama, H.; Urushima, H.; Ozawa, F. J . Organomet. Chem. 2000,
606, 16.
(7) Wen, T. B.; Yang, S. Y.; Zhou, Z. Y.; Lin, Z.; Lau, C. P.; J ia, G.
Organometallics 2000, 19, 3757.
(8) Wen, T. B.; Zhou, Z. Y.; J ia, G. Angew Chem., Int. Ed. 2001, 40,
1951.
(9) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva, M.;
Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carreno, E. Organo-
metallics 1996, 15, 2137.
(10) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa,
J . I. Organometallics 1998, 17, 3479.
10.1021/om034082m CCC: $25.00 © 2003 American Chemical Society
Publication on Web 11/06/2003

5218 Organometallics, Vol. 22, No. 25, 2003
Wen et al.
Sch em e 1
[(η5-arene)OsX(dCdCdCR2)(L)]PF6,12 [(PPh3)2CpOsd
CdCdCHCtC-OsCpPPh3)2]+,13 and [Os(C(CO2Me)d
CH2)(dCdCdCPh2)(CO)(P(i-Pr)3)2]BF4.14
To isolate the vinylidene complex [(PPh3)2ClOs(µ-
Cl)3Os(dCdCHC(OH)Ph2)(PPh3)2] (2), [OsCl2(PPh3)3]
(1) was allowed to react with HCtCC(OH)Ph2 (1:1.2)
in benzene at room temperature for 20 min. The
unreacted 1 was removed by precipitation with ether.
The ether extractant was then stood at RT overnight
to give 2 as brownish yellow microcrystals (Scheme 1).
Isolated 2 is sparingly soluble in benzene and slightly
soluble in CH2Cl2.
To isolate the other products mentioned above, [OsCl2-
(PPh3)3] (1) was allowed to react with HCtCC(OH)Ph2
(1:4) in benzene at room temperature for 30 h. The
reaction produced a small amount of a brown microc-
rystalline solid and a brown solution. The brown solid
was identified to be the facial isomer of the trichlorovi-
nylcarbyne complex fac-[OsCl3(tC-CHdCPh2)(PPh3)2]
(3a ). From the brown solution, the greenish meridonal
trichlorovinylcarbyne complex mer-[OsCl3(tC-CHd
CPh2)(PPh3)2] (3b) can be isolated by recrystallization.
As indicated by the 31P{1H} NMR spectrum, the reaction
also produced several other products, including a small
amount of the carbonyl-containing allenylidene complex
[OsCl2(dCdCdCPh2)(CO)(PPh3)2] (4). Unfortunately,
we have not been able to isolate them in pure form from
the reaction mixture.
Complex 2 has been characterized by elemental
analyses, NMR spectroscopy, and X-ray diffraction. The
crystallographic details and selected bond distances and
angles are given in Tables 1 and 2, respectively. A view
of the molecular geometry of 2 is shown in Figure 1.
The coordination geometry around each osmium center
can be described as a distorted octahedron. The Os(1)-
C(1)-C(2) unit is nearly linear with an angle of
171.2(11)°. The Os(1)-C(1) and C(1)-C(2) bond dis-
tances are at 1.844(14) and 1.303(16) Å, respectively,
which are well comparable with those reported for other
osmium vinylidene complexes.15-22 The hydroxyl proton
Resu lts a n d Discu ssion
Rea ction of [OsCl2(P P h 3)3] w ith HCtCC(OH)P h 2.
The reaction of [OsCl2(PPh3)3] (1) with HCtCC(OH)-
Ph2 (1:2) in C6D6 at room temperature has been moni-
tored by NMR spectroscopy. After [OsCl2(PPh3)3] (1) was
mixed with HCtCC(OH)Ph2 for 20 min, the 31P{1H}
NMR spectrum showed the signals of the starting
material 1 (∼50%), the liberated PPh3, and the di-
nuclear monovinylidene complex [(PPh3)2ClOs(µ-Cl)3Os-
(dCdCHC(OH)Ph2)(PPh3)2] (2). Two small doublet 31P
signals of an unknown species at 3.1 and -15.0 ppm
(J (PP) ) 11.5 Hz) also appeared at this moment. The
signals of 2 grew up first in further reaction and then
decreased with gradual consumption of the starting
materials, while those due to the later unknown complex
grew up gradually along with the signals of the carbyne
complex mer-[OsCl3(tCCHdCPh2)(PPh3)2] (3b) and the
carbonyl allenylidene complex [OsCl2(dCdCdCPh2)-
(CO)(PPh3)2] (4). After 24 h, the 31P NMR spectrum
became very complicated, showing the major signals of
3b, 4, the above-mentioned unknown complex, and
another unknown signal at -40.2 ppm in a ratio of ca.
2:1:4:1. A small amount of fac-[OsCl3(tCCHdCPh2)-
(PPh3)2] (3a ) was precipitated out in the NMR tube.
While complexes 2, 3, and 4 can be isolated from
preparative scale reactions, the products with 31P
signals at 3.1, -15.0, and -40.2 ppm cannot be isolated
in pure form and characterized.
(11) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.;
Lo´pez, A. M.; Modrego, J .; On˜ate, E.; Vela, N. Organometallics 2000,
19, 2585.
(12) Weberndo¨rfer, B.; Werner, H. J . Chem. Soc., Dalton Trans.
2002, 1479.
(13) Xia, H. P.; Ng, W. S.; Ye, J . S.; Li., X. Y.; Wong W. T.; Lin, Z.;
Yang, C.; J ia, G. Organometallics 1999, 18, 4552.
(14) Bohanna, C.; Callejas, B.; Edwards, A. J .; Esteruelas, M. A.;
Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C. Organometallics 1998,
17, 373.
(15) Gusev, D. G.; Maxwell, T.; Dolgushin, F. M.; Lyssenko, M.;
Lough, A. J . Organometallics 2002, 21, 1095.
(16) Baya, M.; Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Modrego,
J .; On˜ate, E. Organometallics 2001, 20, 4291.

Reactions of [OsCl2(PPh3)3] with HCtCC(OH)Ph2
Organometallics, Vol. 22, No. 25, 2003 5219
Ta ble 1. Cr ysta llr ogr a sp h ic Deta ils for Com p lexes 2, 3a , 3b, 4, a n d 6
2‚1.5CH2Cl2
3a ‚1/2CH2Cl2
3b‚3CH2Cl2
4
6‚CH2Cl2
empirical formula
C
87H72Cl4OOs2P4‚
1.5CH2Cl2
C
51H41Cl3OsP2‚
1/2CH2Cl2
C
51H41Cl3OsP2‚
3CH2Cl2
C
52H40Cl2OOsP2
C
51H43BCl2F4OOsP2‚
CH2Cl2
fw
1906.92
293(2)
0.71073
monoclinic
P21/n
19.385(7)
24.464(8)
19.910(6)
90
90.000(7)
90
9442(5)
4
1054.79
294(2)
0.71073
triclinic
P1h
10.2014(19)
11.842(2)
19.869(4)
80.411(4)
88.742(4)
68.163(4)
2194.8(7)
2
1267.11
100(2)
0.71073
monoclinic
P21/n
12.0745(5)
24.2282(11)
18.1144(8)
90
102.3690(10)
90
5176.2(4)
4
1.626
3.027
2520
1003.88
293(2)
0.71073
monoclinic
P21/n
10.252(2)
28.712(6)
14.822(3)
90
94.057(4)
90
4352.0(15)
4
1166.63
200(2)
0.71073
monoclinic
C2/c
36.139(8)
11.437(2)
24.023(5)
90
102.914(6)
90
9678(4)
8
temperature, K
radiation (Mo KR), Å
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
d
calcd, g cm-3
1.341
2.994
3780
1.596
3.258
1050
1.532
3.165
2000
1.601
2.976
4640
abs coeff, mm-1
F(000)
cryst size, mm3
θ range, deg
0.30 × 0.25 × 0.10 0.28 × 0.20 × 0.18 0.46 × 0.10 × 0.05 0.32 × 0.10 × 0.08 0.38 × 0.08 × 0.05
1.95 to 27.61
63 261
21 734 (Rint
0.1468)
7661
1.99 to27.53
14 771
9944 (Rint
0.0255)
8035
1.43 to28.28
44 935
12 356 (Rint
0.0369)
1.98 to 27.56
29 234
10 031 (Rint
0.0465)
6794
1.74 to 26.51
26964
10050 (Rint
0.0669)
7444
no. of reflns collected
no. of indep reflns
)
)
)
)
)
no. of obsd reflns
(I > 2σ(I))
abs corr
10909
SADABS
SADABS
SADABS
SADABS
SADABS
no. of data/restraints/
params
21 734/11/931
9944/2/530
12 356/0/613
10 031/0/523
10 050/0/586
goodness-of-fit on F2
0.942
0.931
1.035
0.889
1.148
final R indices (I > 2σ(I)) R1 ) 0.0661,
R1 ) 0.0356,
wR2 ) 0.0708
1.472 and -0.890
R1 ) 0.0287,
wR2 ) 0.0634
1.223 and -0.720
R1 ) 0.0366,
wR2 ) 0.0703
1.515 and -1.263
R1 ) 0.0625,
wR2 ) 0.1033
1.934 and -1.958
wR2 ) 0.1666
largest peak and hole,
e Å-3
1.531 and -1.619
Ta ble 2. Selected Bon d Len gth s a n d An gles for
[(P P h 3)2ClOs(µ-Cl)3Os(dCdCHC(OH)P h 2)(P P h 3)2]‚
1.5CH2Cl2 (2‚1.5CH2Cl2)
is weakly hydrogen bonded to one of the bridging Cl
(O(1)‚‚‚Cl(3) ) 3.317(11) Å, O(1)-H(1)‚‚‚Cl(3) ) 164.4°).
There are many reported examples of hydrogen-bonding
interaction involvingcoordinatedhalides,either terminal17-19
or bridging in nature.23
Bond Distances (Å)
Os(1)-C(1)
Os(1)-P(1)
Os(1)-P(2)
Os(1)-Cl(1)
Os(1)-Cl(2)
Os(1)-Cl(3)
C(1)-C(2)
1.844(14)
2.352(4)
2.349(4)
2.528(3)
2.441(4)
2.471(3)
1.303(16)
1.426(14)
Os(2)-Cl(4)
Os(2)-P(3)
Os(2)-P(4)
Os(2)-Cl(1)
Os(2)-Cl(2)
Os(2)-Cl(3)
C(2)-C(3)
2.397(4)
2.281(4)
2.272(4)
2.541(3)
2.410(3)
2.533(3)
1.450(17)
Consistent with the solid state structure, the 31P NMR
spectrum (in CD2Cl2) of 2 displayed four sets of doublet
resonances with equal intensity at -4.2 (d, J (PP) ) 8.6
Hz), -11.4 (d, J (PP) ) 8.6 Hz), -19.7 (d, J (PP) ) 16.7
Hz), and -21.1 (d, J (PP) ) 16.7 Hz) ppm, indicating
the presence of four inequivalent phosphorus nuclei of
a dinuclear structure devoid of symmetry. The presence
of the hydroxyvinylidene ligand is supported by the
appearance of a broad singlet at 2.37 ppm assignable
to the hydroxy proton and a broad singlet at 0.71 ppm
assignable to the vinylidene proton in the 1H NMR
spectrum (in CD2Cl2). The 13C{1H} NMR spectrum was
not collected due to the poor solubility.
C(3)-O(1)
Bond Angles (deg)
C(2)-C(1)-Os(1)
P(2)-Os(1)-P(1)
P(1)-Os(1)-Cl(1)
171.2(11) C(1)-C(2)-C(3)
124.6(13)
97.36(14)
101.71(14) P(4)-Os(2)-P(3)
93.49(13) P(3)-Os(2)-Cl(1) 169.41(12)
P(2)-Os(1)-Cl(1) 102.18(12) P(4)-Os(2)-Cl(1)
P(1)-Os(1)-Cl(2) 166.26(12) P(3)-Os(2)-Cl(2)
89.86(13)
94.34(13)
95.79(12)
93.60(12)
P(2)-Os(1)-Cl(2)
P(1)-Os(1)-Cl(3)
P(2)-Os(1)-Cl(3) 167.95(14) P(4)-Os(2)-Cl(3) 167.93(12)
89.99(13) P(4)-Os(2)-Cl(2)
89.92(12) P(3)-Os(2)-Cl(3)
C(1)-Os(1)-P(1)
C(1)-Os(1)-P(2)
C(1)-Os(1)-Cl(1) 168.0(4)
C(1)-Os(1)-Cl(2)
C(1)-Os(1)-Cl(3)
Cl(2)-Os(1)-Cl(3)
Cl(2)-Os(1)-Cl(1)
Cl(3)-Os(1)-Cl(1)
Os(1)-Cl(1)-Os(2) 84.34(10) Os(2)-Cl(2)-Os(1) 89.10(12)
Os(1)-Cl(3)-Os(2) 85.69(10)
91.0(4)
87.7(4)
P(4)-Os(2)-Cl(4)
P(3)-Os(2)-Cl(4)
Cl(4)-Os(2)-Cl(1)
95.58(13)
98.02(14)
88.93(12)
Complex 2 is presumably formed from the reaction
of the intermediate [OsCl2(dCdCHC(OH)Ph2)(PPh3)2]
96.7(4)
88.9(4)
Cl(4)-Os(2)-Cl(2) 161.98(13)
(17) Castarlenas, E.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; On˜ate,
E. Organometallics 2001, 20, 1545.
(18) Castarlenas, E.; Esteruelas, M. A.; On˜ate, E. Organometallics
2000, 19, 5454.
(19) Esteruelas, M. A.; Oliva´n, M.; On˜ate, E.; Ruiz, N.; Tajada, M.
A. Organometallics 1999, 18, 2953.
(20) Weber, B.; Steinert, P.; Windmu¨ller, B.; Wolf, J .; Werner, H.
J . Chem. Soc., Chem. Commun. 1994, 2595.
Cl(4)-Os(2)-Cl(3)
87.87(12)
78.28(11)
77.16(11)
78.62(11)
78.90(11) Cl(2)-Os(2)-Cl(3)
76.84(12) Cl(2)-Os(2)-Cl(1)
80.01(11) Cl(3)-Os(2)-Cl(1)
(21) Huang, D.; Oliva´n, M.; Huffman, J . C.; Eisenstein, O.; Caulton,
K. G. Organometallics 1998, 17, 4700.
(22) Wen, T. B.; Cheung, Y. K.; Yao, J . Z.; Wong, W. T.; Zhou, Z. Y.;
J ia, G. Organometallics 2000, 19, 3803.
(23) See for example: (a) Steel, P. J . J . Organomet. Chem. 1991,
408, 395. (b) Tosik, A.; Maniukiewicz, W.; Bukowska-Strzyzewska, M.;
Mrozinski, J .; Sigalas, M. P.; Tsipis, C. A. Inorg. Chim. Acta 1991,
190, 193. (b) Mrozek, R.; Rzaczynska, Z.; Sikorska-Iwan, M.; J aroniec,
M.; Glowiak, T. Polyhedron 1999, 18, 2321. (c) Hui, N. H.; Norifusa,
T.; Aoki, K. Polyhedron 1999, 18, 2987.
with unreacted [OsCl2(PPh3)3]. The five-coordinated
vinylidene complex [OsCl2(dCdCHPh)(P(i-Pr)3)2], which
is closely related to the intermediate, has recently been
reported by Esteruelas et al.17 Although many osmium
vinylidene complexes have been reported,15-22,24 com-
plex 2 represents a rare example of chloro-bridged
dinuclear osmium vinylidene complexes. Related ruthe-

5220 Organometallics, Vol. 22, No. 25, 2003
Wen et al.
F igu r e 1. Molecular structure of [(PPh3)2ClOs(µ-Cl)3Os-
(dCdCHC(OH)Ph2)(PPh3)2] (2). The phenyl rings of the
PPh3 ligands are represented by the sphere ‘O’ for clarity.
F igu r e 3. Molecular structure of mer-[OsCl3(tC-CHd
CPh2)(PPh3)2] (3b).
Ta ble 3. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for
fa c-[OsCl3(tC-CHdCP h 2)(P P h 3)2]‚1/2(CH2Cl2)
(3a ‚1/2CH2Cl2) a n d
m er -[OsCl3(tC-CHdCP h 2)(P P h 3)2]‚3CH2Cl2
(3b‚3CH2Cl2)
3a ‚1/2CH2Cl2
3b‚3CH2Cl2
Os(1)-C(1)
1.750(4)
1.405(6)
1.361(6)
2.4224(11) Os(1)-P(1)
2.4100(11) Os(1)-P(2)
2.4723(10) Os(1)-Cl(1)
2.4024(11) Os(1)-Cl(2)
2.4374(11) Os(1)-Cl(3)
168.6(3)
130.0(4)
117.8(4)
123.6(4)
Os(1)-C(1)
1.750(3)
1.395(4)
1.364(4)
2.4334(7)
2.4409(7)
2.4955(6)
2.4162(6)
2.3697(6)
168.4(2)
127.6(3)
119.2(3)
122.4(3)
C(1)-C(2)
C(1)-C(2)
C(2)-C(3)
C(2)-C(3)
Os(1)-P(1)
Os(1)-P(2)
Os(1)-Cl(1)
Os(1)-Cl(2)
Os(1)-Cl(3)
C(2)-C(1)-Os(1)
C(3)-C(2)-C(1)
C(2)-C(3)-C(11)
C(2)-C(3)-C(21)
C(2)-C(1)-Os(1)
C(3)-C(2)-C(1)
C(2)-C(3)-C(11)
C(2)-C(3)-C(21)
C(21)-C(3)-C(11) 118.6(3)
P(1)-Os(1)-P(2) 99.64(4)
Cl(1)-Os(1)-Cl(2) 84.04(4)
Cl(2)-Os(1)-Cl(3) 84.61(4)
Cl(1)-Os(1)-Cl(3) 86.76(4)
P(1)-Os(1)-Cl(1)
P(1)-Os(1)-Cl(2)
P(1)-Os(1)-Cl(3)
P(2)-Os(1)-Cl(1)
P(2)-Os(1)-Cl(2)
P(2)-Os(1)-Cl(3)
C(1)-Os(1)-P(1)
C(1)-Os(1)-P(2)
C(21)-C(3)-C(11) 118.4(2)
P(1)-Os(1)-P(2) 175.87(2)
Cl(1)-Os(1)-Cl(2) 89.87(2)
Cl(3)-Os(1)-Cl(2) 172.78(2)
F igu r e 2. Molecular structure of fac-[OsCl3(tC-CHd
CPh2)(PPh3)2] (3a ).
Cl(2)-Os(1)-P(2)
P(1)-Os(1)-Cl(1)
Cl(3)-Os(1)-P(1)
Cl(2)-Os(1)-P(1)
P(2)-Os(1)-Cl(1)
89.43(2)
87.62(2)
91.94(2)
87.69(2)
89.42(2)
81.49(4)
164.45(4)
88.91(4)
97.04(4)
87.73(4)
171.06(4)
91.38(13)
87.51(13)
nium dinuclear allenylidene complexes [Ru2(µ-Cl)3(dCd
CdCAr2)2(PPh3)4]PF6 and [Ru2(µ-Cl)2Cl2(dCdCdCPh2)2-
(TPPMS)4]4- have recently been reported by Dixneuf et
al.2 and Peruzzini et al.,5e respectively.
Cl(3)-Os(1)-Cl(1) 82.91(2)
Cl(3)-Os(1)-P(2)
C(1)-Os(1)-P(1)
C(1)-Os(1)-P(2)
90.55(2)
90.21(9)
92.74(9)
The molecular structures of complexes 3a and 3b
have also been confirmed by X-ray diffraction studies.
The crystallographic details and selected bond distances
and angles are given in Tables 1 and 3, respectively.
The molecular geometries of 3a and 3b are shown in
Figures 2 and 3, respectively. The osmium center in
each complex has a distorted octahedral geometry. In
complex 3a , the two PPh3 ligands are in a cis-arrange-
ment (P(1)-Os-P(2), 99.64(4)°) and the three chloride
ligands are also mutually cis-disposed with one of them
being trans to the carbyne ligand. In complex 3b, the
two PPh3 ligands are trans to each other, occupying the
C(1)-Os(1)-Cl(1) 172.08(13) C(1)-Os(1)-Cl(1) 177.81(9)
C(1)-Os(1)-Cl(2) 102.67(13) C(1)-Os(1)-Cl(2) 89.81(9)
C(1)-Os(1)-Cl(3) 89.67(13)
C(1)-Os(1)-Cl(3) 97.40(9)
axial positions, and the three chlorides and the vinyl-
carbyne ligand lie in the equatorial plane. The Os-
C(carbyne) bond distances and the Os-C(1)-C(2) bond
angles in both complexes (1.750(4) Å and 168.6(3)° in
3a , 1.750(3) Å and 168.4(2)° in 3b) are almost identical,
which are comparable to those reported previously for
other osmium-carbyne complexes.19,20,25-29 The C(1)-
C(2) and C(2)-C(3) bond distances in both complexes
(1.405(6) and 1.361(6) Å in 3a , 1.395(4) and 1.364(4) Å
(24) For additional examples of recent work on Os vinylidene
complexes, see for example: (a) Baya, M.; Esteruelas, M. A. Organo-
metallics 2002, 21, 2332. (b) Castarlenas, R.; Esteruelas, M. A.; On˜ate,
E. Organometallics 2001, 20, 3283. (c) Baya, M.; Esteruelas, M. A.;
On˜ate, E. Organometallics 2001, 20, 4875. (d) Ferrando, G.; Ge´rard,
H.; Spivak, G. J .; Coalter, J . N., III; Huffman, J . C.; Eisenstein, O.;
Caulton, K. G. Inorg. Chem. 2001, 40, 6610. (e) Marchenko, A. V.;
Ge´rard, H.; Eisenstein, O.; Caulton, K. G. New J . Chem. 2001, 25, 1244.
(25) Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A. I.; On˜ate, E.
Organometallics 2003, 22, 414.
(26) Barrio, P.; Esteruelas, M. A.; On˜ate, E. Organometallics 2002,
21, 2491.
(27) Werner, H.; J ung, S.; Weberno¨rfer, B.; Wolf, J . Eur. J . Inorg.
Chem. 1999, 951.

Reactions of [OsCl2(PPh3)3] with HCtCC(OH)Ph2
Organometallics, Vol. 22, No. 25, 2003 5221
Ta ble 4. Selected Bon d Len gth s a n d Bon d An gles
in 3b) as well as the bond angles around C(2) and C(3)
atoms (117.8(4) and 130.0(4)° in 3a , 118.4(2)° and
127.6(3)° in 3b) are consistent with the vinylcarbyne
formulation. The P(1)-Os-P(2) angle of 3a (99.64(4)°)
is significantly deviated from the ideal value of 90°, due
to the steric interaction of the phenyl groups of the PPh3
ligands.
for [OsCl2(dCdCdCP h 2)(CO)(P P h 3)2] (4)
Bond Distances (Å)
Os(1)-C(1)
C(1)-C(2)
Os(1)-P(1)
Os(1)-Cl(1)
C(4)-O(1)
1.898(4)
1.235(6)
2.4346(11)
2.4494(12)
1.116(5)
Os(1)-C(4)
C(2)-C(3)
Os(1)-P(2)
Os(1)-Cl(2)
1.866(5)
1.356(6)
2.4296(12)
2.4505(12)
The solid state structures of 3a and 3b are fully
supported by their solution NMR spectroscopic data. In
the 31P{1H} NMR spectra, complex 3a displayed a
singlet at -14.6 ppm (in CD2Cl2), while complex 3b
displayed a singlet at -16.0 ppm (in CD2Cl2). The most
characteristic spectroscopic features in the 1H NMR
spectra of 3a and 3b are the signals of the vinyl protons
of CHdCPh2, which appeared as triplets at 3.10 ppm
(J (PH) ) 3.5 Hz, in CD2Cl2) for 3a and 4.25 ppm (J (PH)
) 2.1 Hz, in CD2Cl2) for 3b. The 13C{1H} spectrum (in
CD2Cl2) of 3a exhibited a triplet at 267.4 ppm for
OstC (J (PC) ) 15.7 Hz) and two singlets at 167.3 and
131.7 ppm for the vinyl carbons CHdCPh2 and CHd
CPh2, respectively. The 13C{1H} spectrum (in CD2Cl2)
of 3b showed a triplet at 266.3 ppm for OstC (J (PC) )
11.4 Hz) and two singlets at 163.1 and 131.8 ppm for
the vinyl carbons CHdCPh2 and CHdCPh2, respec-
tively.
Reported compounds closely related to 3a and 3b
include [OsCl3(tCR)(PPh3)2] (R ) Me, CH2CMe3),7,8
[OsHCl2(tCR′)(PR3)2] (R ) Cy, i-Pr),27,29,30 [OsCl2(tC-
CHdCRPh)(P(i-Pr)2CH2CO2Me)(P(i-Pr)2CH2CO2)] (R )
Ph, Me),20 and [OsCl2(SCN)(tCC6H4NMe2)(PPh3)2].31 In
all the previously reported complexes, the two PR3
ligands are trans to each other. Complex 3a appears to
be the first [OsX3(tCR)(PR′3)2] complex with two cis PR3
ligands.
Bond Angles (deg)
P(1)-Os(1)-P(2)
P(1)-Os(1)-Cl(1)
P(1)-Os(1)-Cl(2)
C(1)-Os(1)-P(1)
C(1)-Os(1)-P(2)
177.58(4)
86.35(4)
86.29(4)
94.11(12) C(4)-Os(1)-P(1)
85.80(12) C(4)-Os(1)-P(2)
Cl(1)-Os(1)-Cl(2)
P(2)-Os(1)-Cl(1)
P(2)-Os(1)-Cl(2)
89.99(5)
93.91(4)
91.30(4)
94.32(13)
88.10(13)
172.0(5)
88.69(19)
116.8(4)
87.43(15)
C(2)-C(1)-Os(1) 173.4(4)
O(1)-C(4)-Os(1) 178.9(4)
C(2)-C(3)-C(11) 122.7(4)
C(1)-C(2)-C(3)
C(1)-Os(1)-C(4)
C(2)-C(3)-C(21)
C(1)-Os(1)-Cl(1) 176.12(12) C(4)-Os(1)-Cl(1)
C(1)-Os(1)-Cl(2)
93.89(12) C(4)-Os(1)-Cl(2) 177.30(15)
at -15.8, -12.4 ppm are due to 3b and 4, respectively.
These complexes can be isolated in 27% and 16% yield,
respectively, by fractional crystallization followed by
column chromatography. The third product with a 31P
signal at -1.9 ppm could not be isolated in pure form
and identified. In addition, we also isolated the organic
compound 1,1-diphenylethylene (5) from the reaction
mixture, which could be formed from the hydrolysis of
an allenylidene ligand in the reaction (see below). 5 has
1
been characterized by MS and H NMR. In particular,
the FAB-MS displayed the expected molecular ion peak
1
at m/z ) 180.1, and the H NMR spectrum (in CDCl3)
is identical to the reported one,32 showing a singlet at
5.59 ppm with an integration ratio of 1:5 relative to
those of the aromatic proton signals. This reaction also
produced another organic compound, which shows a
characteristic singlet 1H NMR signal at 6.11 ppm (in
C6D6) and a molecular ion peak at m/z ) 398 in the
FAB-MS spectrum. On the basis of the 1H NMR and
MS data, we tentatively assign it as CPh2dCdCHCt
CC(OH)Ph2.
During the course of collecting the 13C and 1H-13C
COSY NMR spectra of 3a , it was found that 3a slowly
isomerizes to 3b at room temperature. As indicated by
1
the 31P and H NMR spectra, ca. 8% of 3a is converted
to 3b after an initially pure sample of 3a in CD2Cl2 was
allowed to stand at RT for 20 h. The isomerization was
completed if a solution of 3a in CHCl3 was refluxed for
1 h. The isomerization is probably not surprising, as it
is anticipated that the cis-arrangement of the two PPh3
ligands in 3a is thermodynamically less favorable due
to the steric repulsion between the two bulky PPh3
ligands.
As mentioned previously, the carbonyl allenylidene
complex 4 was produced in the reaction of [OsCl2-
(PPh3)3] with HCtCC(OH)Ph2. At room temperature,
the compound was formed slowly as a minor product,
and it is difficult to isolate the compound. To encourage
the formation of 4, the reaction has been carried out in
refluxing toluene. The reaction also produced a mixture
of products. The three major phosphorus-containing
products showed singlet 31P signals at -15.8, -12.4, and
-1.9 ppm in a ratio of ca. 4:2:1 (in C6D6). The signals
The solid state structure of complex 4 has also been
determined by an X-ray diffraction study. The crystal-
lographic details and selected bond distances and angles
are given in Tables 1 and 4, respectively. A view of the
molecular geometry of 4 is shown in Figure 4, which
reveals that 4 contains an allenylidene and a carbonyl
ligand. The overall geometry around osmium in 4 can
be described as a distorted octahedron with the two
PPh3 ligands at the axial positions. The equatorial
positions are occupied by the two cis-disposed Cl atoms,
CO, and allenylidene ligands. The diphenylallenylidene
ligand is bound to the metal in a nearly linear fashion
with Os-C(1)-C(2) and C(1)-C(2)-C(3) angles of
173.4(4)° and 172.0(5)°, respectively. The Os-C(1) bond
distance of 1.898(4) Å is about 0.05 Å shorter than that
found in the complex [Os(C(CO2Me)dCH2)(dCdCd
CPh2)(CO)(P(i-Pr3)2]BF4 (1.947(6) Å),14 but is statisti-
cally identical to the values found in osmium-alle-
nylidene complexes [CpOsCl(dCdCdCPh2)(P(i-Pr)3)]
(1.875(6) Å),10 [(η5-C9H7)Os(dCdCdCPh2)(PPh3)2]PF6
(1.895(4) Å),9 and [(η6-mes)OsCl(dCdCdCPh2)(PMe3)]-
PF6 (1.90(1) Å).12 The C(1)-C(2) bond length of 1.235-
(6) Å compares well with those reported for the four
previously structurally characterized osmium alle-
(28) (a) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Mart´ınez, M.
P.; Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 4500.
(b) Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J . I. Organome-
tallics 1997, 16, 4657.
(29) Espuelas, J .; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz,
N. J . Am. Chem. Soc. 1993, 115, 4683.
(30) Spivak, G. J .; Coalter, J . N.; Oliva´n, M.; Eisenstein, O.; Caulton,
K. G. Organometallics 1998, 17, 999.
(31) Clark, G. R.; Edmonds, N. R.; Pauptit, R. A.; Roper, W. R.;
Waters, J . M.; Wright, A. H. J . Organomet. Chem. 1983, 244, C57.
(32) Pouchert, C. J .; Behmke, J . The Aldrich Library of 13C and 1H
FT NMR Spectra, 1st ed.; 1993; Vol. 2, p 37B.

5222 Organometallics, Vol. 22, No. 25, 2003
Wen et al.
Sch em e 2
F igu r e 4. Molecular structure of [OsCl2(dCdCdCPh2)-
(CO)(PPh3)2] (4).
nylidene complexes (1.250(8),14 1.222(9),101.265(6),9 and
1.27(1)12 Å, respectively). However, it is significantly
shorter than the bond length expected for a CdC double
bond (1.30 Å), indicating a substantial contribution of
the canonical form [Os]--CtC-C+Ph2 to the structure
of 4. A similar conclusion has been reached in the
structural analysis of other allenylidene complexes.9,10,12,14
Consistent with the solid state structure, the 13C{1H}
NMR spectrum of 4 displayed a triplet at 278.0 ppm
with a J (PC) of 8.9 Hz assignable to the R-carbon of the
allenylidene ligand and two singlets at 208.1 and 156.3
ppm assignable to the corresponding â- and γ-carbons,
respectively. The presence of the CO ligand is supported
by the triplet 13C{1H} resonance at 173.4 ppm with a
J (PC) of 8.2 Hz. The 31P{1H} NMR spectrum (in C6D6)
displayed a singlet at -12.4 ppm.
Com m en ts on th e F or m a tion of 3 a n d 4 in th e
Rea ction of [OsCl2(P P h 3)3] w ith HCtCC(OH)P h 2.
Reaction of [OsCl2(PPh3)3] with HCtCC(OH)Ph2 in
refluxing toluene was previously reported to give the
allenylidene complex [OsCl2(dCdCdCPh2)(PPh3)2] in
98% isolated yield. However, the allenylidene complex
could be not obtained, in our hand, from the reaction
carried out either in refluxing toluene or in benzene at
room temperature. Instead, we have isolated the di-
nuclear complex [(PPh3)2ClOs(µ-Cl)3Os(dCdCHC(OH)-
Ph2)(PPh3)2], the carbyne complexes fac-[OsCl3(tC-
CHdCPh2)(PPh3)2] (3a ) and mer-[OsCl3(tC-CHd
CPh2)(PPh3)2] (3b), and the carbonyl-containing allenyli-
dene [OsCl2(dCdCdCPh2)(CO)(PPh3)2] (4). The alle-
nylidene complex [OsCl2(dCdCdCPh2)(PPh3)2], how-
ever, could serve as the intermediate for the formation
of 3 and 4.
A plausible mechanism for the formation of 4 is shown
in Scheme 2. Reaction of 1 with HCtCC(OH)Ph2
initially produces the dinuclear hydroxyvinylidene com-
plex 2, which has been isolated. 2 can react with
additional HCtCC(OH)Ph2 to generate [OsCl2(dCdCH-
(C(OH)Ph2)(PPh3)2] (A). The hydroxyvinylidene A then
can undergo dehydration to give the allenylidene com-
plex [OsCl2(dCdCdCPh2)(PPh3)2] (B). Reactions of
1-alkynols with late transition metal complexes via
hydroxyvinylidene intermediates have proven to be one
of the most convenient routes to allenylidene deriva-
tives.33,34 For example, reaction of [RuCl2(PPh3)3] with
HCtCC(OH)Ph2 in the presence of NaPF6 in dichlo-
romethane produces the bimetallic complex [Ru2(µ-Cl)3-
(dCdCdCPh2)2(PPh3)4]PF6,2 reaction of [RuCl2(PPh3)3]
with HCtCC(OH)Ph2 in refluxing THF produces
the 3-phenyl-1-indenylidene complex [RuCl2(C10H5Ph)-
(PPh3)2], which is presumably formed by intramolecular
rearrangement of an allenylidene intermediate,3,4 and
reaction of HCtCC(OH)Ph2 with [RuCl2(PPh3)3] in the
presence of PCy3 in refluxing THF produces the alle-
nylidene complex [RuCl2(dCdCdCPh2)(PCy3)2].4 Nu-
cleophilic addition of water (generated from dehydra-
tion) to the CR-Câ double bond of the allenylidene B
could produce the hydroxycarbene complex C. Addition
of water to CR-Câ of allenylidene ligands to give
hydroxycarbene complexes has been reported for the
reactions of water with [CpRu(dCdCdCPh2)(CO)(P-
35
(i-Pr)3)]BF4 and [Re(dCdCdCHPh)(CO)(MeC(CH2-
PPh2)3)]OTf.36 The hydroxycarbene intermediate C may
(33) Selegue, J . P. Organometallics 1982, 1, 217.
(34) (a) Bruce, M. I. Chem. Rev. 1991, 91, 197. (b) Bruce, M. I. Chem.
Rev. 1998, 98, 2797. (c) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res.
1999, 32, 311.
(35) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
(36) Bianchini, C.; Mantovani, N.; Marvelli, L.; Peruzzini, M.; Rossi,
R.; Romerosa, A. J . Organomet. Chem. 2001, 617-618, 233.

Reactions of [OsCl2(PPh3)3] with HCtCC(OH)Ph2
Organometallics, Vol. 22, No. 25, 2003 5223
Sch em e 3
rearrange to the hydrido-acyl intermediate D, which
could undergo deinsertion of CO to give hydrido-vinyl
complex E. Subsequent reductive elimination of CH2d
CPh2 would give OsCl2(CO)(PPh3)2 (F ). The organic
compound CH2dCPh2 has been isolated and character-
ized by MS and1H NMR in our study. Reaction of F with
HCtCC(OH)Ph2 can then lead to the allenylidene
complex 4 via the hydroxyvinylidene intermediate G.
Reactions of allenylidene complexes with water to give
carbonyl complexes have been recently reported by
Bianchini et al.37 They have shown that the ruthenium
allenylidene complex fac,cis-[RuCl2(dCdCdCPh2)(PNP)]
(PNP ) MeCH2CH2N(CH2CH2PPh2)2) reacts with water
to produce the carbonyl derivative [RuCl2(CO)(PNP)]
and free CH2dCPh2 via regioselective cleavage of the
CR-Câ bond. In this system, use of D2O gives the
corresponding deuterated D2CdCPh2, indicating that
both terminal hydrogens come from water.
Ta ble 5. Selected Bon d Len gth s a n d Bon d An gles
for [OsCl2(tC-CHdCP h 2)(H2O)(P P h 3)2]BF 4‚CH2Cl2
(6‚CH2Cl2)
Formation of the trichlorovinylcarbyne complexes 3a
and 3b from the reaction could be related to the
protonation of vinylidene or allenylidene intermediates
(A or B) by HCl. The HCl could be generated by
dehydrochlorination of the osmium starting material.
We have previously shown that reaction of [OsCl2-
(PPh3)3] with HCtCCMe3 leads to the formation of the
dehydrochlorinated complex [OsClC(CtCCMe3)dCH-
CMe3)(dCdCHCMe3)(PPh3)2] and the trichlorocarbyne
complex [OsCl3(tCCH2CMe3)(PPh3)2].7 The dehydro-
chlorinated complexes [Os(CtCSiMe3)(C(CtCSiMe3)d
CHSiMe3)(dCdCHSiMe3)(PPh3)2] and [OsCl(C(CtCSi-
Me3)dCHSiMe3)(dCdCHSiMe3)(PPh3)2] were also pro-
duced in the reaction of [OsCl2(PPh3)3] with HCt
CSiMe3.8 Thus it is reasonable to speculate that dehy-
drochlorination might also occur in the reaction of
[OsCl2(PPh3)3] with HCtCC(OH)Ph2, although we could
not isolate the dehydrochlorinated products from the
reaction. The low yields of complexes 3 and 4 can be
related to the formation of dehydrochlorinated species.
As mentioned previously, the reaction of [OsCl2(PPh3)3]
with HCtCC(OH)Ph2 also led to the formation of an
organic compound, which is tentatively formulated as
CPh2dCdCHCtCC(OH)Ph2. This compound could be
generated by acetylide-allenylidene coupling through
the intermediate [OsCl(CtCC(OH)Ph2)(dCdCdCPh2)-
(PPh3)2].
Rea ction of [OsCl2(P P h 3)3] w ith HCtCC(OH)P h 2
in th e P r esen ce of Acid s. To prove that formation of
the trichlorovinylcarbyne complexes 3a and 3b is re-
lated to the presence of acid, we have carried out the
reaction of [OsCl2(PPh3)3] with HCtCC(OH)Ph2 in the
presence of HCl. Indeed, treatment of [OsCl2(PPh3)3]
with HCtCC(OH)Ph2 in the presence of HCl resulted
in the formation of a mixture of fac- and mer-trichloro-
vinylcarbyne isomers 3a and 3b as the only products
(Scheme 3). Interestingly, reaction of [OsCl2(PPh3)3]
with HCtCCMe3 in the presence of HCl produces only
mer-[OsCl3(tCCH2CMe3)(PPh3)2].7
Bond Distances (Å)
Os(1)-P(1)
Os(1)-Cl(1)
Os(1)-C(1)
C(1)-C(2)
2.4387(18)
2.3626(19)
1.735(6)
1.420(9)
1.482(9)
Os(1)-P(2)
Os(1)-Cl(2)
Os(1)-O(1)
C(2)-C(3)
2.4447(18)
2.3516(17)
2.209(5)
1.348(10)
1.474(9)
C(3)-C(11)
C(3)-C(21)
Bond Angles (deg)
174.32(6)
P(1)-Os(1)-P(2)
Cl(2)-Os(1)-Cl(1) 158.51(7)
C(1)-Os(1)-O(1) 178.9(3)
C(2)-C(1)-Os(1)
172.4(6)
91.8(2)
C(1)-Os(1)-P(1)
92.8(2)
C(1)-Os(1)-P(2)
C(1)-Os(1)-Cl(2) 101.3(2)
86.59(13) O(1)-Os(1)-P(2)
78.97(15) O(1)-Os(1)-Cl(2)
C(1)-Os(1)-Cl(1) 100.1(2)
O(1)-Os(1)-P(1)
O(1)-Os(1)-Cl(1)
Cl(1)-Os(1)-P(1)
Cl(2)-Os(1)-P(1)
C(3)-C(2)-C(1)
88.79(13)
79.62(15)
87.26(7)
90.45(6)
118.3(6)
88.60(6)
91.98(6)
126.8(7)
Cl(1)-Os(1)-P(2)
Cl(2)-Os(1)-P(2)
C(2)-C(3)-C(11)
C(2)-C(3)-C(21) 123.1(7)
C(21)-C(3)-C(11) 118.6(6)
vinylcarbyne complexes 3a and 3b may involve both
electrophilic abstraction of the OH group of the hydroxy-
vinylidene intermediate [OsCl2(dCdCHC(OH)Ph2)-
(PPh3)2] (A) and protonation of the allenylidene inter-
mediate [OsCl2(dCdCdCPh2)(PPh3)2] (B), with the
former being favored.
Even the weak acid HPPh3BF4 promotes the forma-
tion of carbyne complexes. Thus treatment of [OsCl2-
(PPh3)3] with HCtCC(OH)Ph2 in the presence of HPPh3-
BF4 produced the aqua carbyne complex [OsCl2(tCCHd
CPh2)(H2O)(PPh3)2]BF4 (6).
Complex 6 has been characterized by elemental
analyses and NMR spectroscopy as well as X-ray dif-
fraction study. The crystallographic details and selected
bond distances and angles are given in Tables 1 and 5,
respectively. A view of the molecular geometry of 6 is
shown in Figure 5. The osmium center in 6 has a
distorted octahedral geometry with two trans PPh3
ligands. The vinylcarbyne ligand is trans to the coordi-
nated water molecule (C(1)-Os-O(1) ) 178.9(3)°), while
the two Cl atoms are also mutually trans-disposed,
bending toward the water molecule (Cl(1)-Os-Cl(2) )
158.51(7)°). The short Os-C(1) bond distance (1.735(6)
Å) and the Os-C(1)-C(2) bond angle (172.4(6)°) in 5
are fully consistent with carbyne character,19,20,25-29
which are comparable to those in complexes 3a and 3b
(1.750(4) Å and 168.6(3)° in 3a , 1.750(3) Å and 168.4-
(2)° in 3b). The C(1)-C(2) and C(2)-C(3) bond distances
(1.420(9) and 1.348(10) Å, respectively) are in the
expected range for vinylcarbyne formulation. One of the
hydrogen atoms of the coordinated water molecule is
When the reaction was carried out with DCl (99% D,
20 wt % in D2O solution), the isolated carbyne complexes
have ca. 30% deuterium incorporated at the vinyl group
of 3a and 3b, as indicated by the 1H and 2H NMR
spectra. The results suggest that formation of the
(37) Bianchini, C.; Peruzzini, M.; Zanobini, F.; Lopez, C.; de los Rios,
I.; Romerosa, A. Chem. Commun. 1999, 443.

5224 Organometallics, Vol. 22, No. 25, 2003
Wen et al.
(PPh3)3]39 and HCtCC(OH)Ph2 were prepared according to
the literature methods. All other reagents were used as
purchased from Aldrich Chemical Co.
40
Microanalyses were performed by M-H-W Laboratories
(Phoenix, AZ). 1H, 13C{1H}, and 31P{1H} NMR spectra were
collected on a J EOL EX-400 spectrometer (400 MHz) or a
Bruker ARX-300 spectrometer (300 MHz). 1H and 13C NMR
shifts are relative to TMS, and 31P chemical shifts relative to
85% H3PO4. MS spectra were recorded on a Finnigan TSQ7000
spectrometer.
[(P P h 3)2ClOs(µ-Cl)3Os(dCdCHC(OH)P h 2)(P P h 3)2] (2).
A mixture of [OsCl2(PPh3)3] (0.50 g, 0.48 mmol) and HCtCC-
(OH)Ph2 (0.12 g, 0.58 mmol) in benzene (10 mL) was stirred
at room temperature for 20 min. The volume of the reaction
mixture was reduced to ca. 1 mL. Addition of ether (30 mL) to
the residue gave a green precipitate and a brown solution,
which were separated by filtration. The green precipitate was
identified to be the starting material [OsCl2(PPh3)3], which was
washed with ether (2 × 10 mL) and dried under vacuum (0.36
g). The ether washing solution and the brown filtrate were
collected together, and the volume was reduced to half. The
solution was stored at RT overnight to give a brownish-yellow
microcrystalline solid, which was collected by filtration, washed
with ether (2 × 5 mL), and dried under vacuum. Yield: 46
mg, 11%. 31P{1H} NMR (121.5 MHz, CD2Cl2): δ -4.2 (d, J (PP)
) 8.6 Hz), -11.4 (d, J (PP) ) 8.6 Hz), -19.7 (d, J (PP) ) 16.7
F igu r e 5. Molecular structure of the cation of [OsCl2-
(tC-CHdCPh2)(H2O)(PPh3)2]BF4 (5).
-
hydrogen bonded to one of the F atoms of the BF4
counteranion (O(1)‚‚‚F(1) ) 2.677(8) Å, O(1)-H(1A)‚‚‚
F(1) ) 164.4°). Hydrogen bonding between coordinated
-
water and uncomplexed BF4 anion has been reported
1
Hz), -21.1 (d, J (PP) ) 16.7 Hz). H NMR (300.13 MHz, CD2-
previously for other complexes.38
Cl2): δ 0.71 (br, 1 H, OsdCdCH), 2.37 (br, 1 H, disappeared
when treated with D2O, C(OH)Ph2), 6.70-7.66 (m, 70 H, C6H5,
PPh3). Anal. Calcd for C87H72Cl4P4OOs2: C, 58.72; H, 4.08.
Found: C, 58.90; H, 4.14.
The solution NMR spectroscopic data are consistent
with the coordination sphere of 6 as determined by the
X-ray diffraction study. In particular, the 1H NMR
spectrum (in CD2Cl2) displayed a triplet at 5.07 ppm
(J (PH) ) 1.5 Hz) assignable to the vinyl proton CHd
CPh2. The 13C{1H} NMR spectrum (in CD2Cl2) showed
a triplet at 281.0 ppm for OstC (J (PC) ) 10.4 Hz) and
two singlets at 168.6 and 131.8 ppm for the vinyl
carbons CHdCPh2 and CHdCPh2, respectively. The 31P-
{1H} NMR spectrum displayed only a singlet at 0.2 ppm.
The hydrogen bonding is apparently broken in solution,
as the 19F NMR spectrum of 6 in CD2Cl2 showed only a
fa c-[OsCl3(tC-CHdCP h 2)(P P h 3)2] (3a ) a n d m er -[OsCl3-
(tC-CHdCP h 2)(P P h 3)2] (3b) fr om th e Reaction of [OsCl2-
(P P h 3)3] w ith 1,1-Dip h en ylp r op yn -1-ol a t RT. A solution
of [OsCl2(PPh3)3] (0.50 g, 0.48 mmol) and 1,1-diphenylpropyn-
1-ol (0.40 g, 1.9 mmol) in benzene (10 mL) was stirred for 30
min and then allowed to stand at room temperature for 30 h
to give a brownish solution and a small amount of brown
precipitate, which were separated by filtration. The brown
microcrystalline solid was washed with ether (2 × 3 mL), dried
under vacuum, and identified to be 3a . Yield: 10 mg, 2%. 31P-
{1H} NMR (121.5 MHz, CD2Cl2): δ -14.6 (s). 1H NMR (300.13
MHz, CD2Cl2): δ 3.10 (t, J (PH) ) 3.5 Hz, 1 H, CHdCPh2),
6.71-8.03 (m, 40 H, C6H5, PPh3). 13C{1H} NMR (100.4 MHz,
CD2Cl2): δ 267.4 (t, J (PC) ) 15.7 Hz, OstC), 167.3 (s, CHd
CPh2), 131.7 (s, CHdCPh2), 139.3-127.8 (m, PPh3, C6H5).
Anal. Calcd for C51H41Cl3P2Os: C, 60.51; H, 4.08. Found: C,
60.90; H, 4.54. FAB-MS (NBA, m/z): 977.1 ([M - Cl]+). The
filtrate obtained above was concentrated to ca. 1 mL, and
hexane (30 mL) was added slowly with stirring to give a brown
precipitate, which was filtered, washed with ether (2 × 10 mL)
and hexane (2 × 15 mL), and subsequently dried under
vacuum. Recrystallization of the crude product in 1 mL of
benzene provided green crystals of 3b, which were collected
by filtration, washed with ether (5 mL), and dried under
vacuum overnight. Yield: 43 mg, 9%. 31P{1H} NMR (121.5
-
singlet at -153.0 ppm for the BF4 counteranion. The
closely related osmium aqua-carbyne complex [OsCl2-
(tCC6H4NMe2)(H2O)(PPh3)2]+ was reported by Roper in
1983.31
The allenylidene complex [OsCl2(dCdCdCPh2)(PPh3)2]
was previously reported to be isolated in 98% yield from
the reaction of [OsCl2(PPh3)3] with HCtCC(OH)Ph2. In
our study, however, the allenylidene complex could not
be obtained. Instead, we have isolated several new
osmium complexes including the dinuclear complex
[(PPh3)2ClOs(µ-Cl)3Os(dCdCHC(OH)Ph2)(PPh3)2], tri-
chlorovinylcarbyne complexes fac-[OsCl3(tC-CHdCPh2)-
(PPh3)2] and mer-[OsCl3(tC-CHdCPh2)(PPh3)2], and
the carbonyl-containing allenylidene complex [OsCl2-
(dCdCdCPh2)(CO)(PPh3)2].
1
MHz, CDCl3): δ -16.1 (s). H NMR (300.13 MHz, CDCl3): δ
4.25 (t, J (PH) ) 2.2 Hz, 1 H, CHdCPh2), 7.08-7.88 (m, 40 H,
C6H5, PPh3). 13C{1H} NMR (100.4 MHz, CD2Cl2): δ 266.3 (t,
J (PC) ) 11.4 Hz, OstC), 163.1 (s, CHdCPh2), 131.8 (s, CHd
Exp er im en ta l Section
All manipulations were carried out under a nitrogen atmo-
sphere using standard Schlenck techniques unless otherwise
stated. Solvents were distilled under nitrogen from sodium
benzophenone (hexane, ether, THF), sodium (benzene), or
calcium hydride (CH2Cl2). The starting materials [OsCl2-
CPh2), 139.4-127.4 (m, PPh3, C6H5). Anal. Calcd for C51H41
-
Cl3P2Os: C, 60.51; H, 4.08. Found: C, 60.35; H, 4.18. FAB-
MS (NBA, m/z): 977.1 ([M - Cl]+).
m er -[OsCl3(tC-CH dCP h 2)(P P h 3)2] (3b) a n d [OsCl2-
(CO)(dCdCdCP h 2)(P P h 3)2] (4) fr om t h e R ea ct ion of
[OsCl2(P P h 3)3] w ith 1,1-Dip h en ylp r op yn -1-ol in Reflu x-
(38) See for example: (a) Funaioli, T.; Cavazza, C.; Marchetti, F.;
Fachinetti, G. Inorg. Chem. 1999, 38, 3361. (b) Leung, W. H.; Chan,
E. Y. Y.; Wong, W. T. Inorg. Chem. 1999, 38, 136. (c) Sanford, M. S.;
Henling, L. M.; Grubbs, R. H. Organometallics 1998, 17, 5384. (d) Mui,
H. D.; Brumaghim, J . L.; Gross, C. L.; Girolami, G. S. Organometallics
1999, 18, 3264.
(39) Hoffmann, P. R.; Caulton, K. G. J . Am. Chem. Soc. 1975, 97,
4221.
(40) J ones, E. R. H.; Lee, H. H.; Whiting, M. C. J . Chem. Soc. 1960,
3483.

Reactions of [OsCl2(PPh3)3] with HCtCC(OH)Ph2
Organometallics, Vol. 22, No. 25, 2003 5225
in g Tolu en e. A mixture of [OsCl2(PPh3)3] (0.60 g, 0.57 mmol)
and 1,1-diphenylpropyn-1-ol (0.27 g, 1.3 mmol) in toluene (60
mL) was refluxed for 3 h to give a brownish-red solution. The
solvent was removed under vacuum, and the resulting oil was
dissolved in CH2Cl2 (2 mL). Addition of hexane (50 mL) to the
residue gave a brown precipitate, which was collected by
filtration, washed with hexane (2 × 20 mL), and dried under
vacuum (0.51 g). The brown filtrate and the washing solution
were also collected and evaporated to dryness under vacuum
to give a brownish oil, which was extracted with 20 mL of
hexane and filtered. The hexane extractant was reduced to
ca. 2 mL and then passed through a silica gel column using
hexane as the eluting solvent. The light yellow first eluant
was collected. Removal of the solvent gave a drop of light
yellow oil, which was identified to be CH2dCPh2 (5). 1H NMR
(300.13 MHz, CDCl3): δ 5.59 (s, 2 H, CH2), 7.43-7.49 (m, 10
H, Ph). FAB-MS (NBA, m/z): 180.1 (M+). The brown solid
obtained above was transferred to a Schlenk tube and treated
with 2 mL of benzene. The solution was allowed to stand at
room temperature for 1 day to give 3b as a green microcrys-
talline solid, which was separated from the mother liquid,
washed with ether (2 mL), and dried under vacuum overnight.
Yield: 0.13 g, 23%. The mother liquid and the ether washing
solution were collected together and dried under vacuum. The
residue was extracted with 2 mL of benzene and passed
through a silica gel column (1.5 × 20 cm). Elution with benzene
gave a mixture of CH2dCPh2 (5) and CPh2dCdCH-CtC-
C(OH)Ph2. Spectroscopic data for CPh2dCdCH-CtC-C(OH)-
concentrated to ∼3 mL, and ether (30 mL) was added slowly
with stirring to give a green precipitate, which was collected
by filtration, washed with ether (2 × 20 mL), and dried under
vacuum overnight. The solid was identified to be 3b. Yield:
0.22 g, 45%.
[OsCl2(tC-CHdCP h 2)(H2O)(P P h 3)2]BF 4 (6). A mixture
of [OsCl2(PPh3)3] (0.50 g, 0.48 mmol), 1,1-diphenylpropyn-1-
ol (0.21 g, 0.96 mmol), and HPPh3BF4 (0.44 g, 1.26 mmol) in
CH2Cl2 (15 mL) and benzene (10 mL) was stirred for 8 h to
give a green precipitate. The volume of the solution was
reduced to one-half. The green solid was collected by filtration,
washed with ether (3 × 30 mL), and dried under vacuum
overnight. Yield: 0.31 g, 59%. 31P{1H} NMR (121.5 MHz, CD2-
Cl2): δ 0.2 (s). 1H NMR (300.13 MHz, CD2Cl2): δ 5.07 (t, J (PH)
) 1.5 Hz, 1 H, CHdCPh2), 6.80-7.69 (m, 40 H, C6H5, PPh3).
13C{1H} NMR (100.4 MHz, CD2Cl2): δ 281.0 (t, J (PC) ) 10.4
Hz, OstC), 168.6 (s, CHdCPh2), 131.8 (s, CHdCPh2), 138.6-
127.6 (m, PPh3, C6H5). 19F NMR (282.4 MHz CD2Cl2): δ -153.0
(s). IR (KBr, cm-1): ν(OH) 3500 (m), ν(BF) 1086 (s). Anal. Calcd
for C51H43BCl2F4OP2Os: C, 56.63; H, 4.01. Found: C, 56.74;
H, 4.40.
Cr ysta l Str u ctu r e An a lyses. Crystals suitable for X-ray
diffraction were grown from CH2Cl2 solutions of 2, 3a , 3b, 4,
and 6 layered with hexane. Data collections were performed
on a Bruker SMART CCD area detector for 2, 3a , and 4 and
on a Bruker Apex CCD area detector for 3b and 6, by using
graphite-monochromated Mo KR radiation (λ ) 0.71073 Å).
Empirical absorption corrections (SADABS)41 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)42
program package. All non-hydrogen atoms were refined aniso-
tropically. The solvating CH2Cl2 molecules in 2 and one of the
CH2Cl2 solvent molecules in 3b are disordered and were
refined with suitable restraints. The H atom of the OH group
in 2 and those of the coordinated water molecule in 6 were
located from the difference Fourier maps and constrained to
ride on the respective O atom. The remaining 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 1.
1
Ph2 are as follows. H NMR (300.13 MHz, C6D6): δ 6.11 (s, 1
H, dCH), 7.04-7.66 (m, 20 H, Ph). FAB-MS (NBA, m/z): 398
(M+). After the column was further flushed with benzene to
wash away the yellow polymers and oligomers, CH2Cl2 was
used to elute 4 as a brick-red solution. The solvent was
removed completely to give a brownish-red solid. Yield: 0.089
g, 16%. An analytically pure sample of 4 can be obtained by
recrystllization from CH2Cl2/hexane. 31P{1H} NMR (121.5
MHz, C6D6): δ -12.4(s). 1H NMR (300.13 MHz, C6D6): δ 6.96-
7.12 (m, 22 H, m-C6H5, PPh3), 7.48 (t, J (HH) ) 7.4 Hz, 2 H,
p-C6H5), 7.76 (d, J (HH) ) 7.7 Hz, 2 H, o-C6H5), 8.35 (m, 12 H,
PPh3). 13C{1H} NMR (100.4 MHz, CD2Cl2): δ 278.0 (t, J (PC)
) 8.9 Hz, OsdC), 208.1 (s, OsdCdC), 173.4 (t, J (PC) ) 8.2
Hz, Os-CO), 156.3 (s, OsdCdCdC), 146.8-128.0 (m, PPh3,
C6H5). Anal. Calcd for C52H40Cl2OP2Os: C, 62.21; H, 4.02.
Found: C, 62.26; H, 4.17. After the brick-red complex 4 was
eluted, the column was washed with CH2Cl2/ether to give a
brownish-green solution, followed by removal of solvent and
recrystallization from benzene to give additional green complex
3b (23 mg, total yield 27%).
Rea ction of [OsCl2(P P h 3)3] w ith 1,1-Dip h en ylp r op yn -
1-ol in th e P r esen ce of HCl. To a solution of [OsCl2(PPh3)3]
(0.50 g, 0.48 mmol) and 1,1-diphenylpropyn-1-ol (0.30 g, 1.4
mmol) in CH2Cl2 (15 mL) was added HCl‚OEt2 (1.50 mL, 1.5
mmol, 1.0 M in ether solution). The reaction mixture was
stirred at room temperature for 8 h to give a brownish-green
solution. The volume of the solution was reduced to ca. 1 mL,
and benzene (20 mL) was added slowly with stirring to give a
yellowish-green microcrystalline solid. The mixture was stirred
for 20 min, and the solid was collected by filtration, washed
with ether (2 × 20 mL), and dried under vacuum overnight; it
was identified to be 3a . Yield: 78 mg, 16%. The filtrate was
Ack n ow led gm en t. The authors acknowledge finan-
cial support from the Hong Kong Research Grants
Council.
Su p p or tin g In for m a tion Ava ila ble: Tables of bond
distances and angles, atomic coordinates and equivalent
isotropic displace coefficients, and anisotropic displacement
coefficients for [(PPh3)2ClOs(µ-Cl)3Os(dCdCHC(OH)Ph2)-
(PPh3)2] (2), fac-[OsCl3(tC-CHdCPh2)(PPh3)2] (3a ), mer-
[OsCl3(tC-CHdCPh2)(PPh3)2] (3b ), [OsCl2(dCdCdCPh2)-
(CO)(PPh3)2] (4), and [OsCl2(tC-CHdCPh2)(H2O)(PPh3)2]BF4
(6). This material is available free of charge via the Internet
at http://pubs.acs.org.
OM034082M
(41) Sheldrick G. M. SADABS, Empirical Absorption Correction
Program; University of Go¨ttingen: Germany, 1996.
(42) Bruker. SHELXTL Reference Manual (Version 5.1); Bruker
Analytical X-Ray Systems Inc.: Madison, WI, 1997.