Vinylidene and carbyne complexes derived from the reactions of OsCl(PPh3)(PCP) (PCP = 2,6-(PPh2CH2)2C6H3) with terminal acetylenes

Article abstract of DOI:10.1021/om000150i

Treatment of OsCl₂(PPh₃)₃ with 1,3-(PPh₂CH₂)₂C₆H₄ led to the formation of the coordinatively unsaturated complex OsCl(PPh₃)(PCP) (PCP = 2,6-(PPh₂

Full text of DOI:10.1021/om000150i

Organometallics 2000, 19, 3803-3809
3803
Vin ylid en e a n d Ca r byn e Com p lexes Der ived fr om th e
Rea ction s of OsCl(P P h )(P CP ) (P CP )
3
2
,6-(P P h CH ) C H ) w ith Ter m in a l Acetylen es
2
2 2
6
3
†
†
†
‡
Ting Bin Wen, Yuk King Cheung, J unzhi Yao, Wing-Tak Wong,
§
,†
Zhong Yuan Zhou, and Guochen J ia*
Department of Chemistry, The Hong Kong University of Science and Technology,
Department of Chemistry, The University of Hong Kong, and Department of Applied Biology
and Chemical Technology, Hong Kong Polytechnic University, Hong Kong, China
Received February 15, 2000
Treatment of OsCl
natively unsaturated complex OsCl(PPh
OsCl(PPh )(PCP) with RCtCH (R ) Ph, t-Bu, C(OH)Ph
Treatment of OsCl(dCdCHPh)(PPh )(PCP) and OsCl(dCdCHC(OH)Ph
HCl produced the carbyne complexes OsCl (tCCH Ph)(PCP) and OsCl (tCCHdCPh
respectively. The solid-state structures of OsCl(PPh )(PCP) and OsCl(dCdCHPh)(PPh
2
(PPh
3
)
3
with 1,3-(PPh
)(PCP) (PCP ) 2,6-(PPh
) gave OsCl(dCdCHR)(PPh
)(PPh )(PCP) with
)(PCP),
)-
2
CH
2
)
2
C
6
H
4
led to the formation of the coordi-
CH ). Reactions of
)(PCP).
3
2
2 2 6 3
) C H
3
2
3
3
2
3
2
2
2
2
3
3
(PCP) have been determined by X-ray diffraction.
In tr od u ction
We have recently shown that reactions of RuCl-
PPh3)(PCP) (PCP ) 2,6-(PPh2CH2)2C6H3) with terminal
acetylenes RCtCH lead to the formations of the un-
(
Reactions of terminal acetylenes HCtCR with coor-
dinatively unsaturated compounds could often lead to
4
usual coupling products RuCl(PPh3)(η -RCHdC-2,6-
1
vinylidene complexes. It has also been established that
1
0a,b
(PPh2CH2)2C6H3) (eq 1).
Although not observed, the
vinylidene complexes LnMR′(dCdCHR) can undergo
C-R′ bond formation reactions via migratory insertion
reactions of R′ to the R-carbon of the vinylidene ligand.
2
This implies that reactions of HCtCR with transition
metal complexes LnM-R′ may go though vinylidene
intermediates LnM-R′(dCdCHR) to give vinyl com-
plexes LnM-R′CdCHR. In fact, coupling reactions
between acetylide and vinylidene ligands have been
reported for many reactions of HCtCR with certain
vinylidene complexes RuCl(dCdCHR)(PPh3)(PCP) were
3
complexes to give η -R3CHR complexes and catalytic
dimerization or oligomerization reactions of terminal
(
4) (a) Wakatsuki, Y.; Yamazaki, H.; Kumegawa, N.; Satoh, T.;
3
-5
acetylenes.
Although interesting, examples of cou-
Satoh, J . Y. J . Am. Chem. Soc. 1991, 113, 9604. (b) Wakatsuki, Y.;
Yamazaki, H. J . Organomet. Chem. 1995, 500, 349. (c) Wakatsuki, Y.;
Yamazaki, H.; Kumegawa, N.; J ohar, P. S. Bull. Chem. Soc. J pn. 1993,
66, 987. (d) Wakatsuki, Y.; Satoh, M.; Yamazaki, H. Chem. Lett. 1989,
pling between vinylidene and other ligands such as
6
7-9
hydride, alkyl, vinyl,
and aryl ligands in the reac-
1
585.
5) (a) Yang, S. M.; Chan, M. C. W.; Cheung, K. K.; Che, C. M.; Peng,
tions of terminal acetylenes with transition metal
complexes are still rather limited.
(
S. M. Organometallics 1997, 16, 2819. (b) Yi, C. S.; Liu, N. Organo-
metallics 1996, 15, 3968. (c) Slugovc, C.; Mereiter, K.; Zobetz, E.;
Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275. (d) Albertin,
G.; Antoniutti, S.; Bordignon, E. J . Chem. Soc., Dalton Trans. 1995,
719. (e) Albertin, G.; Antoniutti, S.; Del Ministro, E.; Bordignon, E. J .
Chem. Soc., Dalton Trans. 1992, 3203. (f) Albertin, G.; Amendola, P.;
Antoniutti, S.; Ianelli, S.; Pelizzi, G.; Bordignon, E. Organometallics
1991, 10, 2876. (g) Hills, H.; Hughes, D. L.; J imenez-Tenorio, M.; Leigh,
G. J .; McGeary, C. A.; Rowley, A. T.; Bravo, M.; McKenna, C. E.;
McKenna, M. C. J . Chem. Soc., Chem. Commun. 1991, 522. (h) Hughes,
D. L.; J imenez-Tenorio, M.; Leigh, G. J .; McGeary, C. A.; Rowley, A.
T. J . Chem. Soc., Dalton Trans. 1993, 3151. (i) J ia, G.; Meek, D. W.
Organometallics 1991, 10, 1444. (j) Field, L. D.; George, A. V.; Hambley,
T. W. Inorg. Chem. 1990, 29, 4563.
†
The Hong Kong University of Science and Technology.
The University of Hong Kong.
Hong Kong Polytechnic University.
‡
§
(1) (a) Bruce, M. I. Chem. Rev. 1991, 91, 197. (b) Bruce, M. I.;
Swincer, A. G. Adv. Organomet. Chem. 1983, 22, 59. (c) Bruneau, C.;
Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311.
(2) See for example: (a) Oliv a´ n, M.; Clot, E.; Eisenstein, O.; Caulton,
K. G. Organometallics 1998, 17, 3091. (b) Bianchini, C.; Innocenti, P.;
Peruzzini, M.; Romerosa, A.; Zanobini, F. Organometallics 1996, 15,
2
4
72. (c) Braun, T.; Meuer, P.; Werner, H. Organometallics 1996, 15,
075. (d) Wiedemann, R.; Wolf, J .; Werner, H. Angew. Chem., Int. Ed.
Engl. 1995, 34, 1244. (e) Wiedemann, R.; Steinert, P.; Sch a¨ fer, M.;
Werner, H. J . Am. Chem. Soc. 1993, 115, 9864. (f) Sch a¨ fer, M.; Mahr,
N.; Wolf, J .; Werner, H. Angew. Chem., Int. Ed. Engl. 1993, 32, 1315.
(6) (a) Buil, M. L.; Esteruelas, M. A. Organometallics 1999, 18, 1798.
(b) Esteruelas, M. A.; Oro, L. A.; Valero, C. Organometallics 1995, 14,
3596.
(g) Fryzuk, M. D.; Huang, L.; McManus, N. T.; Paglia, P.; Rettig, S.
J .; White, G. S. Organometallics 1992, 11, 2979. (h) McMullen, A. K.;
Selegue, J . P.; Wang, J . G. Organometallics 1991, 10, 3421.
(7) Huang, D.; Oliv a´ n, M.; Huffman, J . C.; Eisenstein, O.; Caulton,
K. G. Organometallics 1998, 17, 4700.
(8) Selnau, H. E.; Merola, J . S. J . Am. Chem. Soc. 1991, 113, 4008.
(9) Werner, H.; Sch a¨ fer, M.; Wolf, J .; Peters, K.; Von Schnering, H.
G. Angew. Chem., Int. Ed. Engl. 1995, 34, 191.
(3) (a) Bianchini, C.; Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini,
F. Organometallics 1994, 13, 4616. (b) Barbaro, P.; Bianchini, C.;
Peruzzini, M.; Polo, P.; Zanobini, F.; Frediani, P. Inorg. Chim. Acta
1
994, 220, 5. (c) Bianchini, C.; Bohanna, C.; Esteruelas, M. A.; Frediani,
P.; Meli, A.; Oro, L. A.; Peruzzini, M. Organometallics 1992, 11, 3837.
d) Bianchini, C.; Peruzzini, M.; Zanobini, F.; Frediani, P.; Albinati,
A. J . Am. Chem. Soc. 1991, 113, 5453.
(10) (a) J ia, G.; Lee, H. M.; Xia, H. P. Williams, I. D. Organometallics
1996, 15, 5453. (b) Lee, H. M.; Yao, J . Z.; J ia, G. Organometallics 1997,
16, 3927. (c) J ia, G.; Lee, H. M.; Xia, H. P. Williams, I. D. J . Organomet.
Chem. 1997, 534, 173.
(
1
0.1021/om000150i CCC: $19.00 © 2000 American Chemical Society
Publication on Web 08/17/2000

3
804 Organometallics, Vol. 19, No. 19, 2000
Wen et al.
proposed to be the intermediates for the coupling
reactions. These reactions represent rare examples of
coupling between aryl and vinylidene ligands in the
reactions of LnM-Ar with terminal acetylenes. To see
if similar coupling reactions would also occur and if the
vinylidene intermediates could be observed with related
osmium system, we have prepared the analogous os-
mium complex OsCl(PPh3)(PCP) and investigated its
reactivity toward HCtCR (R ) Ph, t-Bu, C(OH)Ph2).
We have been able to isolate the vinylidene complexes
OsCl(dCdCHR)(PPh3)(PCP) from the reactions. The
vinylidene complexes, however, do not undergo similar
coupling reactions, but can be used to prepare osmium
carbyne complexes.
Resu lts a n d Discu ssion
P r ep a r a tion a n d Sp ectr oscop ic Ch a r a cter iza -
tion of OsCl(P P h 3)(P CP ). The coordinatively unsat-
urated complex OsCl(PPh3)(PCP) (5) was prepared by
the reaction of OsCl2(PPh3)3 (3) with ligand 4 in 2-pro-
panol (eq 2). Formally one molecule of HCl was elimi-
F igu r e 1. Molecular structure for OsCl(PPh3)(PCP). The
thermal ellipsoids are shown at the 50% probability level.
Ta ble 1. Cr ysta l Da ta a n d Refin em en t Deta ils for
3
OsCl(P P h )(P CP ) (5) a n d
OsCl(dCdCHP h )(P P h
3
)(P CP )‚H
2
2
O (6‚H O)
5
6‚H
2
O
formula
fw
cryst sys
space group
a, Å
C
50
H
42ClP
961.46
monoclinic
P2 /a (#14)
3
Os
C
58
H
48ClP Os‚H O
3
2
1081.54
monoclinic
P2 /n
13.6143(11)
16.4298(13)
22.1628(17)
96.276(2)
4927.7(7)
4
nated from the reaction. The reaction is quite similar
to the preparation of the analogous complex RuCl(PPh3)-
1
1
1
0a,11
12
(
PCP)
addition to ruthenium,
with PCP or related phosphine ligands have been
and RuCl(PPh3)((2,6-P(i-Pr)2CH2)2C6H3). In
14.042(1)
17.496(2)
17.082(2)
95.74(2)
4175.6(7)
4
1.529
0.07107
47.9
1
0-12
b, Å
c, Å
a large number of complexes
â, deg
1
3
previously reported for Rh, Pt, Pd, Ir, and Ni.
3
V, Å
The spectroscopic data of the green compound 5 is
Z
d
calc, g cm-
3
1.458
0.071073
55.08
consistent with a square-pyramidal complex with PPh3
radiation, Mo KR, Å
3
1
1
occupying the apical position. In particular the P{ H}
NMR spectrum of the green compound 5 in C6D6 showed
a doublet at 27.9 ppm for the PPh2 groups and a triplet
at 7.9 ppm (J (PP) ) 11.3 Hz) for the PPh3 ligand.
Virtual doublet of triplet signals at 3.57 and 2.46 ppm
2
θ max, deg
scan type
ω
7058
ω
no. of reflns collected
no. of ind reflns
no. of obsd reflns
no. of params refined
final R indices
32 732
6754 (Rint ) 4.4%) 11 316 (Rint ) 10.49%)
4439 (F > 3σ(F))
496
R ) 5.4%,
R
2.51
2.99
-2.80
7351 (F > 4σ(F))
578
1
were observed in the H NMR spectrum (in C6D6) for
R ) 4.83%,
(obsd data)
w
) 7.0%
w
R ) 10.70%
the methylene protons, indicating that the two PPh2
goodness of fit
0.937
1.480
-1.105
groups are trans to each other.14
-3
largest diff peak, e Å
largest diff hole, e Å-
3
(11) (a) Karlen, T.; Dani, P.; Grove, D. M.; Steenwinkel, P.; van
Koten, G. Organometallics 1996, 15, 5687. (b) Dani, P.; Karlen, T.;
Gossage, R. A.; Smeets, W. J . J .; Spek, A. L.; van Koten, G. J . Am.
Chem. Soc. 1997, 119, 11317. (c) Steenwinkel, P.; Kolmschot, R. A.;
Gossage, R. A.; Dani, P.; Veldman, N.; Spek, A. L.; van Koten, G. Eur.
J . Inorg. Chem. 1998, 477.
Ta ble 2. Selected Bon d Dista n ces a n d An gles for
OsCl(P P h )(P CP )
3
Bond Distances (Å)
Os(1)-Cl(1)
Os(1)-P(2)
Os(1)-C(1)
2.427(4)
2.313(4)
2.04(1)
Os(1)-P(1)
Os(1)-P(3)
2.312(4)
2.231(4)
(
12) van der Boom, M. E.; Kraatz, H. B.; Hassner, L.; Ben-David,
Y.; Milstein, D. Organometallics 1999, 18, 3873.
13) For additional recent work on complexes with PCP and related
(
ligands, see for example: (a) Liou, S. Y.; van der Boom, M. E.; Milstein,
D. Chem. Commun. 1998, 687. (b) van der Boom, M. E.; Ben-David,
Y.; Milstein, D. Chem. Commun. 1998, 917. (c) Vigalok, A.; Shimon,
L. J . W.; Milstein, D. J . Am. Chem. Soc. 1998, 120, 477. (d) van der
Boom, M. E.; Liou, S. Y.; Ben-David, Y.; Shimon, L. J . W.; Milstein, D.
J . Am. Chem. Soc. 1998, 120, 6531. (e) Vigalok, A.; Uzan, O.; Shimon,
L. J . W.; Ben-David, Y.; Martin, J . M. L.; Milstein, D. J . Am. Chem.
Soc. 1998, 120, 12539. (f) van der Boom, M. E.; Liou, S. Y.; Ben-David,
Y.; Gozin, M.; Milstein, D. J . Am. Chem. Soc. 1998, 120, 13415. (f)
Vigalok, A.; Rybtchinski, L. B.; Shimon, L. J . W.; Ben-David, Y.;
Milstein, D. Organometallics 1999, 18, 895. (g) van der Boom, M. E.;
Higgitt, C. L.; Milstein, D. Organometallics 1999, 18, 2413. (h) Lee,
D. W.; Kasaka, W. C.; J ensen, C. M. Organometallics 1998, 17, 1. (i)
Liu, F.; Pak, E. B.; Singh, B.; J ensen, C. M.; Goldman, A. S. J . Am.
Chem. Soc. 1999, 121, 4086.
Bond Angles (deg)
Cl(1)-Os(1)-P(1)
Cl(1)-Os(1)-P(3)
P(1)-Os(1)-P(2)
P(1)-Os(1)-C(1)
P(2)-Os(1)-C(1)
94.8(1)
122.6(1)
149.9(1)
78.6(4)
Cl(1)-Os(1)-P(2)
Cl(1)-Os(1)-C(1)
P(1)-Os(1)-P(3)
P(2)-Os(1)-P(3)
P(3)-Os(1)-C(1)
91.9(1)
152.7(4)
102.6(1)
98.4(1)
82.1(4)
84.7(4)
The structure of 5 has been confirmed by an X-ray
diffraction study. The molecular geometry of 5 is
depicted in Figure 1. The crystallographic details and
selected bond distances and angles are given in Tables
and 2, respectively. Overall, the structure is very
similar to that of RuCl(PPh3)(PCP). The structure of
1
1
0c
(14) Wilkes, L. M.; Nelson, J . H.; McCusker, L. B.; Seff, K.; Mathey,
F. Inorg. Chem. 1983, 22, 2476, and references therein.
5 can be viewed as a distorted square pyramid with the

Reactions of OsCl(PPh
3
)(PCP)
Organometallics, Vol. 19, No. 19, 2000 3805
PPh3 ligand located at the apex. The four atoms Cl(1),
P(1), C(1), and P(2) form the base and the osmium
center is above the square base toward the apical
position. The distortion from square pyramid is clearly
indicated by the difference in the P(3)-Os-C(1) (84.7(4)°)
and P(3)-Os-Cl(1) (122.6(1)°) angles. The P(1)-Os-
P(2) angle (149.9(1)°) is significantly smaller than those
expected for complexes with trans-deposited phosphines.
The small angle may be caused by the small bite angle
of the PCP ligand. The small bite angle of the PCP
ligand may also cause P(1)-Os-C(1) (78.6(4)°) and
P(2)-Os-C(1) (82.1(4)°) angles to be significantly smaller
than P(1)-Os-Cl(1) (94.8(1)°) and P(2)-Os-Cl(1)
(91.9(1)°) angles. The Os-C(1) bond length of 2.04(1) Å
is close to those observed for Os-C(aryl) bonds in
complexes such as OsH(C6H4-2-(E-CHdCHPh))(CO)(P(i-
Pr)3)2 (2.136(7) Å),1 Os(C2Ph)(NHdCPhC6H4)(CO)(P(i-
5
1
6
Pr)3)2 (2.089(7) Å), and Os(PyPh-4-Br)Cl(CO)(PPh3)2
(
2.050(9) Å).17
Rea ction s of Com p lex 5 w ith P h CtCH a n d
t-Bu CtCH. Reaction of PhCtCH with complex 5 in
CH2Cl2 produced the vinylidene complex OsCl(dCd
CHPh)(PPh3)(PCP) (6) (eq 3). The structure of complex
F igu r e 2. Molecular structure for OsCl(dCdCHPh)-
(PPh3)(PCP). The thermal ellipsoids are shown at the 40%
probability level.
Ta ble 3. Selected Bon d Dista n ces a n d An gles for
OsCl(dCdCHP h )(P P h
3
2
)(P CP )‚H O
Bond Distances (Å)
Os(1)-Cl(1)
Os(1)-P(2)
Os(1)-C(1)
C(9)-C(10)
2.5128(15)
2.3547(15))
2.133(5)
Os(1)-P(1)
Os(1)-P(3)
Os(1)-C(9)
C(10)-C(11)
2.3889(14)
2.4536(14)
1.819(6)
1.453(9)
1.337(8)
Bond Angles (deg)
C(9)-Os(1)-C(1)
C(9)-Os(1)-P(2)
91.3(2)
C(9)-Os(1)-P(1)
95.53(17)
97.01(17)
78.45(15)
171.58(16)
157.13(5)
83.30(5)
82.63(17) C(9)-Os(1)-P(3)
6
is supported by the NMR data as well as elemental
C(9)-Os(1)-Cl(1) 178.58(16) C(1)-Os(1)-P(1)
analysis. The meridional geometry of the PCP ligand is
C(1)-Os(1)-P(2)
C(1)-Os(1)-Cl(1)
P(1)-Os(1)-P(3)
P(2)-Os(1)-P(3)
P(3)-Os(1)-Cl(1)
78.80(15) C(1)-Os(1)-P(3)
87.10(16) P(1)-Os(1)-P(2)
1
13
supported by the virtual triplet H and C signals of
the CH2 groups.14 The PPh3 is trans to the central
aromatic ring of the PCP ligand, as indicated by the
101.76(5)
101.10(5)
84.58(5)
P(1)-Os(1)-Cl(1)
P(2)-Os(1)-Cl(1)
Os(1)-C(9)-C(10) 173.6(5)
97.92(5)
2
large J (Cipso-PPh3) coupling constant (61.8 Hz). The
C(9)-C(10)-C(11) 126.1(6)
presence of the vinylidene ligand is supported by the
1
3
1
C{ H} NMR spectrum (in CDCl3), which exhibited an
OsdC signal at 303.7 ppm and an OsdCdCH signal at
09.7 ppm. For comparison, the R- and â-carbon signals
of the vinylidene ligand in OsHCl(dCdCHCy)(CO)(P(i-
that in 5. The Os(1)-C(9) and C(9)-C(10) bond dis-
tances and Os-C(9)-C(10) angle are normal compared
to those reported for osmium vinylidene complexes such
1
7
as Os(dCdCHSiMe3)(CHdCHSiMe3)Cl(P(i-Pr)3)2, OsCl2-
6
b
Pr)3)2 were observed at 326.9 and 121.9 ppm,respectively.
The vinylidene proton signal in complex 6 was observed
at 0.91 ppm in the H NMR spectrum (in CDCl3).
1
8
(dCdCHPh)(P(i-Pr)3)(P(i-Pr)2CH2CH2NMe2)],
1
9
1
[Cp*Os(dCdCHCMe3)(CO)(PPh3)]BF4, and Os(dCd
2
0
CC6H8)(CO)2(PPh3)2. It is also interesting to note that
the phenyl group of the vinylidene ligand is oriented
toward the central aromatic ring of the PCP ligand,
probably to minimize the steric interaction with the
PPh3 ligand. Such an orientation is in agreement with
the geometry of the vinyl group in compounds 2 assum-
ing that compounds 2 were formed from RuCl(dCd
CHR)(PPh3)(PCP) with a similar conformation.1
The structure of 6 has been confirmed by an X-ray
diffraction study. The molecular geometry of 6 is
depicted in Figure 2. The crystallographic details and
selected bond distances and angles are given in Tables
1
and 3, respectively. The structure of 6 can be viewed
as a distorted octahedron with a meridional PCP ligand
and a vinylidene ligand trans to a chloride. The distor-
tion could be mainly attributed to the small bite angle
of the PCP ligand as reflected by the P(1)-Os(1)-P(2)
angle (157.13(5)°). The angle is larger than that in
complex 5, but is still significantly smaller than that
expected for trans-deposited phosphines. The Os-
C(aryl) bond distance (2.133(5) Å) is slightly longer than
0a,b
Treatment of complex 5 in CH2Cl2 with t-BuCtCH
produced the analogous vinylidene complex OsCl(dCd
CH(t-Bu))(PPh3)(PCP) (7). The complex has very similar
3
1
P NMR data to 6, implying that the two complexes
have very similar structure. The presence of the vi-
(
15) Esteruelas, M. A.; Lahoz, F. J .; O n˜ ate, E.; Oro, L. A.; Sola, E.
J . Am. Chem. Soc. 1996, 118, 89.
16) Esteruelas, M. A.; Lahoz, F. J .; L o´ pez, A. M.; O n˜ ate, E.; Oro,
L. A. Organometallics 1995, 14, 2496.
17) Clark, A. M.; Rickard, C. E. F.; Roper, W. R.; Wright, L. J .
Organometallics 1999, 18, 2813.
(18) Weber, B.; Steinert, P.; Windm u¨ ller, B.; Wolf, J .; Werner, H.
J . Chem. Soc., Chem. Commun. 1994, 2595.
(19) Pourreau, D. B.; Geoffroy, G. L.; Rheingold, A. L.; Geib, S. J .
Organometallics 1986, 5, 1337.
(20) Roper, W. R.; Waters, J . M.; Wright, L. J . Van Meurs, F. J .
Orgaomet. Chem. 1980, 201, C27.
(
(

3
806 Organometallics, Vol. 19, No. 19, 2000
Wen et al.
1
3
1
nylidene ligand is supported by the C{ H} NMR
spectrum (in CD2Cl2), which exhibited OsdC signal at
Sch em e 1
2
99.3 ppm and OsdCdCH signal at 117.2 ppm, and the
1
H NMR spectrum (in C6D6), which showed the vi-
nylidene proton signal at -0.51 ppm. Complexes of the
formula OsCl(dCdCHR)(PPh3)(PCP) are interesting as
examples of well-characterized complexes with both
vinylidene and alkyl ligands, which are still very
1
limited.
Several mechanisms have been proposed for the
formation of mononuclear vinylidene complexes from the
reactions of coordinatively unsaturated complexes with
terminal acetylenes.21-26 Vinylidene complexes may be
formed intramolecularly from a π-acetylene complex
2
LnM(η -HCtCR) by direct 1,2-hydrogen shift, or from
a hydrido-alkynyl complex LnMH(CtCR) by 1,3-
hydrogen shift of the hydride to the â-carbon of the
alkynyl ligand.2
1,22,26
Vinylidene complexes may also be
days. When a red-brown C6D6 solution of 6 was stood
at room temperature for a week or heated for a day,
partial decomposition of complex 6 occurred to give a
formed though hydrido-alkynyl complexes LnMH(Ct
CR) intermolecularly by a bimolecular hydrogen shift
process23 or by dissociation of a proton from the metal
31
purple solution, which showed only P NMR signals of
center followed by addition of the proton to the â-carbon
complex 6 (major) and Ph3PO (minor). Decomposition
of 6 in commercially available CDCl3 also occurred. Thus
when a CDCl3 solution of 6 was stored at room temper-
ature for a day, a small amount of NMR active species
of the alkynyl ligand.2
4,25
In our case, we have not been
able to detect the expected π-acetylene complexes or the
hydrido-alkynyl complexes. Thus the detailed mecha-
nism is not very clear. However, intermolecular hydro-
gen shift processes are unlikely considering the results
of some deuterium-labeling experiments. Treatment of
OsCl(PPh3)(PCP) with a mixture of PhCtCD and
t-BuCtCH produced OsCl(dCdCDPh)(PPh3)(PCP) and
OsCl(dCdCH(t-Bu))(PPh3)(PCP). Reaction of OsCl-
3
1
1
which shows a singlet P{ H} signal at 14.5 ppm was
3
1
produced along with PPh3. As indicated by in situ P-
1
{ H} NMR, decomposition of 6 is not completed even
after the solution was stored for 3 days. Long storage
of the solution (8 days) led to complete decomposition
of 6 to give a purplish-blue solution, which showed no
3
1
(PPh3)(PCP) with PhCtCH in the presence of D2O
P signals except that of Ph3PO. The initial decomposi-
3
1
1
produced only OsCl(dCdCHPh)(PPh3)(PCP). These re-
sults are inconsistent with intermolecular hydrogen
shift processes, but are consistent with intramolecular
hydrogen shift processes. It is likely that our vinylidene
complexes are formed via OsCl(HCtCR)(PPh3)(PCP) by
a 1,2-hydrogen shift process, as calculations have shown
that the 1,2-hydrogen shift process is usually more
tion product having the P{ H} signal at 14.5 ppm was
identified to be the carbyne complex OsCl2(tCCH2Ph)-
(PCP) (8), which can be readily prepared by treating 6
with aqueous hydrochloric acid (Scheme 1).
Complex 8 was characterized by elemental analysis
and NMR, IR, and MS spectroscopy. The meridional
geometry of the PCP ligand is supported by the virtual
2
1,22
1
13
favorable than the 1,3-hydrogen shift process.
triplet CH signals of the PCP ligand in the H and
C
2
1
4
F or m a tion of Ca r byn e Com p lexes fr om Com p lex
NMR spectra. The presence of the OstCCH2Ph group
is indicated by H and C NMR. In particular, the H
NMR spectrum (in CDCl3) showed the CH2 signal at
1
13
1
6
. As mentioned previously, the complex RuCl(PPh3)-
(
PCP) reacted with PhCtCH to give the coupling
4
13
product RuCl(PPh3)(η -PhCHdC-2,6-(PPh2CH2)2C6H3).
In this reaction, the vinylidene complex RuCl(dCd
CHPh)(PPh3)(PCP) was proposed as the key intermedi-
1.35 ppm, and the C NMR spectrum (in CDCl3) showed
the tC and CH2 signals at 284.2 and 55.0 ppm,
respectively. For comparison, the CH2 proton signal was
1
0b
13
ate, which appears to be too reactive to be observed.
observed at 2.04 ppm and the C signals for tC and
We have tried to induce similar intramolecular coupling
reaction of complex 6 by standing at room temperature
or heating solutions of complex 6 in solvents such as
THF, benzene, or chloroform. However, the expected
coupling product was not observed in the experiments.
CH2 were observed at 264.68 and 56.95 ppm for
2
7a
OsHCl2(tCCH2Ph)(P(i-Pr)3)2. Reported osmium car-
byne complexes closely related to 8 include OsHCl2(t
2
7,28
29
CR)(PR′3)2 (PR′3 ) P(i-Pr)3,
PCy3 ), OsCl2(tC-CHd
CRPh)(P(i-Pr)2CH2CO2Me)(P(i-Pr)2CH2CO2) (R ) Ph,
Me), and OsCl2(SCN)(tCC6H4-NMe2)(PPh3)2.
1
8
30
As indicated by 31P{1H} NMR, no appreciable reaction
In the protonation of 6 with hydrochloric acid, the
carbyne complex 8 was likely formed by protonation of
the vinylidene ligand to give [OsCl(PPh3)(tCCH2Ph)-
occurred when solutions of complex 6 in THF-d8 and
C6D6 were allowed to stand at room temperature for 2
(
(
21) Silvestre, J .; Hoffmann, R. Helv. Chim. Acta 1985, 68, 1461.
22) Wakatsuki, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J . Am.
(27) (a) Espuelas, J .; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz,
N. J . Am. Chem. Soc. 1993, 115, 4683. (b) Bourgault, M.; Castillo, A.;
Esteruelas, M. A.; O n˜ ate, E.; Ruiz, N. Organometallics 1997, 16, 636.
(28) (a) Spivak, G. J .; Coalter, J . N.; Oliv a´ n, M.; Eisenstein, O.;
Caulton, K. G. Organometallics 1998, 17, 999. (b) Spivak, G. J .;
Caulton, K. G. Organometallics 1998, 17, 5260.
(29) Werner, H.; J ung, S.; Webern o¨ rfer, B.; Wolf, J . Eur. J . Inorg.
Chem. 1999, 951.
(30) Clark, G. R.; Edmonds, N. R.; Pauptit, R. A.; Roper, W. R.;
Waters, J . M.; Wright, A. H. J . Organomet. Chem. 1983, 244, C57.
Chem. Soc. 1994, 116, 8105.
23) Wakatsuki, Y.; Koga, N.; Werner, H.; Morokuma, K. J . Am.
Chem. Soc. 1997, 119, 360.
24) Bianchini, C.; Peruzzini, M.; Vacca, A.; Zanobini, F. Organo-
metallics 1991, 10, 3697.
25) (a) De los R ˆı os, I.; J im e´ nez-Tenorio, M.; Pureta, M. C.; Valerga,
(
(
(
P. J . Am. Chem. Soc. 1997, 119, 6529. (b) Bustelo, E.; J im e´ nez-Tenorio,
M.; Pureta, M. C.; Valerga, P. Organometallics 1999, 18, 4563.
(26) Stegmann, R.; Frenking, G. Organometallics 1998, 17, 2089

Reactions of OsCl(PPh
3
)(PCP)
Organometallics, Vol. 19, No. 19, 2000 3807
+
-
(
PCP)] , followed by substitution of the PPh3 with Cl .
Sch em e 2
Formation of 8 from CDCl3 solution of 6 is also likely
initiated by protonation of the vinylidene ligand with
water or a trace amount of acid present in the solvent.
Protonation of vinylidene ligands to give carbyne com-
plexes is one of the typical reactions of vinylidene
1
complexes. To determine if [OsCl(tCCH2Ph)(PPh3)-
+
(
PCP)] was the intermediate in the formation of
complex 8, we have prepared complex [OsCl(tCCH2-
Ph)(PPh3)(PCP)]BF4 (9) by reacting complex 5 with
HBF4‚Et2O and investigated the reactivity of 9 toward
-
Cl . Indeed, 8 was produced rapidly and cleanly on
treatment of 9 with NEt3CH2PhCl. This observation
supports that [OsCl(tCCH2Ph)(PPh3)(PCP)]+ is the
intermediate in the formation of complex 8. Several
monocationic osmium carbyne complexes related to
complex 9 have been reported, for example, [OsCl2(tC-
2
7b
CH2Ph)(H2O)(P(i-Pr3)2]BF4,
[OsCl2(tC-tolyl)(H2O)-
+
30,31
+ 32
(
PPh3)2] ,
OAc)(tCR)(P(i-Pr)3)2] .
During the course of investigating the chemical
[CpOsCl(tCR)(P(i-Pr)3)] , and [OsH-
complexes or coupling product via these intermediates
could be obtained, reaction of Ph2(OH)CCtCH with
complex 5 was investigated. Treatment of Ph2(OH)CCt
CH with complex 5 in CH2Cl2 produced the hydoxyvi-
nylidene complex OsCl(dCdCHC(OH)Ph2)(PPh3)(PCP)
+
33
(
properties of complex 9, it was found that complex 9
reacted with excess water to give complex 6. Thus one
of the CH2 protons of OstCCH2Ph was deprotonated
by water. The deprotonation reaction can be related to
the acidic nature of the protons R to the carbyne carbon.
Deprotonation reactions of protons R to the carbyne
carbons by bases are known reactions. For example,
OsHCl2(tCCH2Ph)(P(i-Pr3)2 can be deprotonated by
(
10) (see Scheme 2). The presence of the vinylidene
1
ligand in complex 10 is indicated by the H NMR
spectrum (in CD2Cl2), which showed the vinylidene
proton signal at 0.84 ppm and the OH signal at 0.32
ppm. The similarity in the coordination spheres of
31
complex 6 and 10 is reflected in their P NMR data.
2
7b
NaOMe to give OsHCl(dCdCHPh)(P(i-Pr3)2, [Cp((CO)2-
Complex 10 is stable in the solid state in an inert
atmosphere. However, it slowly decomposes in solvents
such as CHCl3, THF, and benzene. For example, after
solutions of 10 in C6D6 or CDCl3 were allowed to stand
+
RetCCH3)] can be deprotonated by THF to give Cp-
(
CO)2RedCdCH2,34 and [Cp(CO)2MntC-CHdCPh2)]+
can be deprotonated by water or THF to give Cp-
(
CO)2MndCdCdCPh2.35
31
at room temperature for 2 days, the intensity of the P-
R ea ct ion of Com p lex 5 w it h P h 2(OH )CCtCH .
1
1
31
{
{
H} signals due to 10 decreased, and a new singlet P-
Ph2(OH)CCtCH has often been used as the reagent to
prepare hydroxyvinylidene or allenylidene complexes.
For example, a hydroxyvinylidene complex has been
obtained from its reaction with RuCl2(P(i-Pr)2CH2CO2-
H} signal at 14.6 (in C6D6) or 14.8 ppm (in CDCl3)
appeared along with that of Ph3PO. The new compound
31
having the P chemical shift of 14.8 ppm (in CDCl3)
was identified to be the vinylcarbyne complex OsCl2(t
CCHdCPh2)(PCP) (11), which can be obtained easily by
reacting complex 10 with aqueous HCl. The presence
of the OstCCHdCPh2 group in complex 11 is indicated
3
6
Me)2; allenylidene complexes have been prepared from
+
37
its reactions with complexes such as [CpRu(PMe3)2] ,
+
38
+ 39
[
RuCl(dppm)2] ,
[RuCl(dppe)2] ,
[CpOs(CO)(P(i-
+
40
5
+
41
Pr)3)] , [(η -C9H7)M(PPh3)2] (M ) Ru, Os), [Os(C(CO2-
1
13
1
by H and C NMR. In particular, the H NMR
+
42
Me)dCH2)(OdCMe2)(CO)(P(i-Pr)3)2] , and CpOsCl(P(i-
spectrum (in CD2Cl2) showed a CHd signal at 4.74 ppm,
Pr)3).43 To see if hydroxyvinylidene or allenylidene
13
1
and the C{ H} NMR spectrum (in CD2Cl2) showed d
C, CHd, and dCPh2 signals at 275.0, 131.8, and 154.0
ppm. In the protonation reaction of complex 10 with
aqueous HCl, complex 11 is presumably formed by
(
31) Gallop, M. A.; Roper, W. R. Adv. Organomet. Chem. 1986, 25,
21.
32) Esteruelas, M. A.; L o´ pez, A. M.; Ruiz, N.; Tolosa, J . I. Orga-
nometallics 1997, 16, 4657.
33) Crochet, P.; Esteruelas, M. A.; L o´ pez, A. M.; Mart ´ı nez, M. P.;
Oliv a´ n, M.; O n˜ ate, E.; Ruiz, N. Organometallics 1998, 17, 4500.
34) Kelley, C.; Mercando, L. A.; Terry, M. R.; Lugan, N.; Geoffroy,
G. L.; Xu, Z.; Rheingold, A. L. Angew. Chem., Int. Ed. Engl. 1992, 31,
053.
35) Kolobova, N. E.; Ivanov, L. L.; Zhvanko, O. S.; Khitrova, O. M.;
Batsanov, A. S.; Struchkov, Y. T. J . Organomet. Chem. 1984, 262, 39.
36) Werner, H.; Stark, A.; Steinert, P.; Gr u¨ nwald, C.; Wolf, J . Chem.
Ber. 1995, 128, 49.
1
(
+
electrophilic abstraction of the OH group of 10 by H
(
+
to give [OsCl(tC-CHdCPh2)(PPh3)(PCP)] , followed by
substitution reaction of PPh3 with Cl . In fact, [OsCl-
(
-
1
(tC-CHdCPh2)(PPh3)(PCP)]BF4 (12) could be prepared
by reaction of complex 10 with HBF4 and reacted with
PhCH2NEt3Cl to give complex 11.
(
(
Com m en ts on th e Rea ctivity of HCtCR tow a r d
MCl(P P h 3)(P CP ) (M ) Ru , Os). It is interesting to
note that reactions of RuCl(PPh3)(PCP) with HCtCR
(
(
37) Selegue, J . P. Organometallics 1982, 1, 217.
38) Touchard, D.; Pirio, N.; Dixneuf, P. H. Organometallics 1995,
1
4, 4920.
39) Touchard, D.; Haquette, P.; Daridor, A.; Romero, A.; Dixneuf,
P. H. Organometallics 1998, 17, 3844.
40) Esteruelas, M. A.; G o´ mez, A. V.; Lahoz, F. J .; L o´ pez, A. M.;
O n˜ ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
41) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonz a´ lez-Cueva, M.;
4
(
gave the coupling products RuCl(PPh3)(η -RCHdC-2,6-
(PPh2CH2)2C6H3), while the analogous reactions with
(
OsCl(PPh3)(PCP) produced the vinylidene complexes
OsCl(dCdCHR)(PPh3)(PCP). In the case of ruthenium,
the coupling products are likely produced from the
(
Lastra, E.; Borge, J .; Garc ´ı a-Granda, S.; P e´ rez-Carreno, E. Organo-
metallics 1996, 15, 2137.
(
42) Bohanna, C.; Callejas, B.; Edwards, A. J .; Esteruelas, M. A.;
Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C. Organometallics 1998,
7, 373.
(43) Crochet, P.; Esteruelas, M. A.; L o´ pez, A. M.; Ruiz, N.; Tolosa,
J . I. Organometallics 1998, 17, 3479.
1

3
808 Organometallics, Vol. 19, No. 19, 2000
Wen et al.
vinylidene intermediates RuCl(dCdCHR)(PPh3)(PCP),
although they could not be observed. In the case of
osmium, the vinylidene complexes can be isolated, but
they cannot be converted to the corresponding coupling
products. The difference could be related to the stronger
Os-C and OsdC bonds.44 Ruthenium and osmium
complexes with similar composition may adopt different
was collected by filtration, washed with ether (50 mL) and
hexane (50 mL), and dried under vacuum overnight. Yield:
0
.20 g, 61%. A crystalline sample of 6 could be obtained by
slow evaporation of solvent of a saturated solution of OsCl(d
3
1
1
CdCHPh)(PPh
MHz, CDCl ): δ 6.4 (d, J (PP) ) 11.9 Hz), -8.5 (t, J (PP) )
1.9 Hz). 1H NMR (300.13 MHz, CDCl
): δ 0.91 (br, 1 H,
Ãs)CdCH), 4.10 (dt, J (HH) )15.3 Hz, J (PH) ) 4.4 Hz, 2 H,
CH ), 4.48 (dt, J (HH) ) 15.3 Hz, J (PH) ) 4.0 Hz, 2 H, CH ),
7.60-5.50 (m, 43 H, PPh , PPh , C H , C H ). 13C{
H} NMR
): δ 303.7 (q, J (PC) ) 8.7 Hz, OsdC), 158.0
3
)(PCP) in wet CH
2
Cl
2
.
P{ H} NMR (121.5
3
1
3
2
a,7
isomeric forms that have been noted previously.
For
2
2
2
9
example, OsHCl2(tCCH2Ph)(PR′3)2 (PR′3 ) PCy3, P(i-
Pr)32 ) are carbyne complexes, while RuCl2(dCHCH2-
1
3
2
6
3
6
5
7,28
(75.5 MHz, CDCl
3
4
5
46
Ph)(PR′3)2 (PR′3 ) PCy3, P(i-Pr)3 ) are carbene com-
plexes. Similarly, Os(dCdCHSiMe3)(CHdCHSiMe3)Cl-
(d, J (PC) ) 61.8 Hz, C(aryl)), 146.4-121.4 (m, other aromatic
carbons), 109.7 (s, OsdCdCH), 48.3 (td, J (PC) ) 19.3, 5.3 Hz,
PCP-CH
2
). Anal. Calcd for C58
.66. Found: C, 64.43; H, 4.77. The presence of water in the
H
48ClP
3
2
Os‚H O: C, 64.41; H,
(P(i-Pr)3)2 can be isolated from the reaction of HCt
4
CSiMe3 with OsH3Cl(P(i-Pr)3)2, but the coupling product
sample has been confirmed by an X-ray diffraction study (see
below).
3
[
Ru (η -Me3SiCH dC-CH dCH SiMe3)(CO)(P (t-Bu )2-
+
Me)2] was obtained from the reaction of HCtCSiMe3
OsCl(dCdCH(t-Bu ))(P P h
3
)(P CP ) (7). To a CH
2 2
Cl (60
7
with RuH(OTf)(CO)(P(t-Bu)2Me)2. Concerning the pat-
mL) solution containing OsCl(PPh
3
)(PCP) (0.50 g, 0.52 mmol)
tern of the stability of isomeric forms, Caulton et al.
have recently noted that ruthenium favors structures
with a maximum number of C-C and C-H bonds
within the ligands, while osmium favors structures with
was added tert-butylacetylene (0.19 mL, 1.56 mmol). The
reaction mixture was stirred for 15 min to give a brownish-
red solution. The solvent was evaporated to dryness under
vacuum. A pink solid was obtained when ether (50 mL) was
added. The solid was collected by filtration, washed with ether
2
a
a maximum number of metal-ligands bonds. Our
(
3 × 30 mL), and dried under vacuum overnight to give 0.36
g of crude product (67%). The solid was redissolved in 2 mL of
CH Cl . Slowly addition of hexane (30 mL) to the dichlo-
results fit the pattern well.
2
2
Exp er im en ta l Section
romethane solution produced a pink solid, which was collected
by filtration, washed with ether and hexane, and dried under
All manipulations were carried out under a nitrogen atmo-
sphere using standard Schlenk techniques. Solvents were
distilled under nitrogen from sodium benzophenone (hexane,
vacuum. 31P{ H} NMR (121.5 MHz, C
1
D
): δ 7.5(d, J (PP) )
6
1
6
1
2.8 Hz), -10.9 (t, J (PP) ) 12.8 Hz). H NMR (300.13 MHz,
): δ -0.51 (q, J (PH) ) 3.0 Hz, 1 H, ÃsdCdCH), 0.37 (s,
9 H, CMe ), 4.30 (dt, J (HH) ) 15.5 Hz, J (PH) ) 4.7 Hz, 2 H,
CH ), 4.89 (dt, J (HH) ) 15.5 Hz, J (PH) ) 4.4 Hz, 2 H, CH ),
.96-6.96 (m, 38 H, PPh ). C{ H} NMR (100.40,
MHz, CD Cl ): δ 299.3 (dt, J (PC) ) 6.9, 11.0 Hz, OsdC), 160.6
d, J (PC) ) 73.4 Hz, C(aryl)), 147.2-121.7 (m, other aromatic
carbons), 117.2 (s, OsdCdCH), 49.4 (td, J (PC) ) 19.1, 5.1 Hz,
PCP-CH ). Anal. Calcd for C56 Os: C, 64.45; H, 5.02.
Found: C, 64.60; H, 5.12. FAB-MS (NBA, m/e): 1009 ([M -
6 6
C D
2 2
ether, THF), sodium (benzene), or calcium hydride (CH Cl ).
4
7
48
3
The starting materials OsCl
2
(PPh
3
)
3
,
2 2 2 6 4
1,3-(PPh CH ) C H ,
4
9
2
2
and HCtCC(OH)Ph
2
were prepared according to literature
1
3
1
7
3 2 6 3
, PPh , C H
methods. All other reagents were used as purchased from
Aldrich Chemical Co.
2
2
(
Microanalyses were performed by M-H-W Laboratories
1
13
1
31
1
(
Phoenix, AZ). H, C{ H}, and P{ H} NMR spectra were
2
H52ClP
3
collected on a J EOL EX-400 spectrometer (400 MHz) or a
1
13
Bruker ARX-300 spectrometer (300 MHz). H and C NMR
+
+
3
] ).
3
1
Cl] ), 782 ([M - PPh
OsCl (tCCH P h )(P CP ) (8). A 37% hydrochloric acid solu-
tion (0.04 mL, 0.56 mmol) was added to a CH Cl (50 mL)
solution of OsCl(dCdCHPh)(PPh )(PCP) (0.15 g, 0.14 mmol).
chemical shifts are relative to TMS, and P NMR chemical
shifts relative to 85% H PO . MS spectra were recorded on a
Finnigan TSQ7000 spectrometer.
OsCl(P P h )(P CP ) (5). A mixture of 1,3-(PPh
1.01 g, 2.13 mmol) and OsCl (PPh (1.86 g, 1.77 mmol) in
0 mL of degassed 2-propanol was refluxed for 8 h. The solid
2
2
3
4
2
2
3
2 2 2 6 4
CH ) C H
3
The resulting mixture was stirred at room temperature for 1
h to give a yellowish-green solution. The solvent was evapo-
rated to dryness under vacuum. A light green solid was
obtained when ether (30 mL) was added. The solid was
collected by filtration, washed with ether (2 × 30 mL), and
(
2
3 3
)
5
was collected by filtration, washed with 2-propanol (2 × 50
mL), and dried under vacuum overnight. Yield: 1.1 g, 65%.
3
1
1
P{ H} NMR (121.5 MHz, C
6
D
6
): δ 27.9 (d, J (PP) ) 11.3 Hz),
): δ 8.04-
), 3.57 (dt, J (HH) ) 15.9 Hz,
), 2.46 (dt, J (HH) ) 15.9 Hz, J (PH)
). Anal. Calcd for C50 Os: C, 62.33;
H, 4.60. Found: C, 62.50; H, 4.62.
OsCl(dCdCHP h )(P P h )(P CP ) (6). To a CH
solution containing OsCl(PPh )(PCP) (0.30 g, 0.31 mmol) was
3
1
1
1
dried under vacuum overnight. Yield: 0.096 g, 82%. P{ H}
7
6
.9 (t, J (PP) ) 11.3 Hz). H NMR (300.13 MHz, C
.52 (m, 38 H, PPh , PPh , C H
3 2 6 3
6
D
6
1
NMR (121.5 MHz, CDCl
CDCl ): δ 1.35 (s, 2 H, ÃstCCH
J (PH) ) 4.5 Hz, 2 H, CH ), 4.44 (dt, J (HH) ) 17.7 Hz, J (PH)
5.4 Hz, 2 H, CH ), 8.00-5.92 (m, 28 H, PPh , C , C ).
C{ H} NMR (75.5 MHz, CDCl ): δ 284.2 (t, J (PC) ) 11.4
Hz, OstC), 150.4 (s, C(aryl)), 147.3-122.7 (m, other aromatic
carbons), 55.0 (s, OstCCH ), 45.0 (t, J (PC) ) 18.5 Hz, PCP-
CH ). Anal. Calcd for C40 Os: C, 57. 35; H, 4.09, Cl,
.46. Found: C, 57.26; H, 4.14; Cl, 8.16.
OsCl(tCCH P h )(P P h )(P CP )]BF (9). HBF
mmol, 54% solution in ether) was added to a brownish-red CH
Cl solution (40 mL) of OsCl(dCdCHPh)(PPh )(PCP) (0.30 g,
3
): δ 14.5 (s). H NMR (300.13 MHz,
), 3.44 (dt, J (HH) ) 17.7 Hz,
J (PH) ) 6.1 Hz, 2 H, CH
6.1 Hz, 2 H, CH
2
3
2
)
2
H42ClP
3
2
)
2
2
6
H
3
6 5
H
1
3
1
3
3
2 2
Cl (60 mL)
3
2
added phenylacetylene (0.3 mL, 3.0 mmol). The reaction
mixture was stirred for 30 min to give a brownish-red solution.
The solvent was evaporated to dryness under vacuum. A pink
solid was obtained when ether (50 mL) was added. The solid
2
2 2
H34Cl P
8
[
2
3
4
4
(60 µL, 0.44
2
-
(44) Metal ligand bonds are generally stronger for 5d metals than
2
3
4
6
d metals. Sim o˜ es, J . A. M.; Beauchamp, J . L. Chem. Rev. 1990, 90,
29.
(
0.28 mmol). The reaction mixture was stirred at room tem-
perature for 30 min to give a dark brown solution. The volume
of the reaction mixture was reduced to ca. 5 mL, and ether
45) Wolf, J .; St u¨ er, W.; Gr u¨ nwald, C.; Werner, H.; Schwab, P.;
Schulz, M. Angew. Chem., Int. Ed. Engl. 1998, 37, 1124.
46) Gr u¨ nwald, C.; Gevert, O.; Wolf, J .; Gonz a´ lez-Herrero, P.;
Werner, H. Organometallics 1996, 15, 1960.
47) Hoffmann, P. R.; Caulton, K. G. J . Am. Chem. Soc. 1975, 97,
221.
(20 mL) was added slowly with stirring to give a pale brown
(
solid. The crude product was collected by filtration, washed
(
with ether (2 × 30 mL), and dried under vacuum overnight
4
3
(0.21 g, 65.6%). The crude product was redissolved in 20 mL
(
(
48) Rimml, H.; Venanzi, L. M. J . Organomet. Chem. 1983, 259, C6.
49) J ones, E. R. H.; Lee, H. H.; Whiting, M. C. J . Chem. Soc. 1960,
of THF. After filtration, the filtrate was concentrated in vacuo
to 5 mL. Addition of ether (20 mL) to the residue produced a
483.

Reactions of OsCl(PPh
3
)(PCP)
Organometallics, Vol. 19, No. 19, 2000 3809
pale brown solid, which was collected by filtration, washed
(300.13 MHz, CDCl
) 15.8 Hz, J (PH) ) 4.3 Hz, 2 H, CH
Hz, J (PH) ) 4.8 Hz, 2 H, CH ), 7.6-5.8 (m, 48 H, PPh
). C{ H} NMR (75.5 MHz, CD Cl ): δ 277.5 (q,
3
): δ 3.1 (s, 1 H, ÃstCCH), 3.30 (dt, J (HH)
), 4.43 (dt, J (HH) ) 15.8
, PPh
with ether (3 × 30 mL), and dried under vacuum overnight to
2
3
1
1
give 0.15 g (yield, 46.9%) of product. P{ H} NMR (121.5 MHz,
2
3
2
,
1
3
1
CDCl
3
): δ 11.3 (d, J (PP) ) 13.4 Hz), -12.1 (t, J (PP) ) 13.4
C
6
H
3
, C
6
H
5
2
2
1
Hz). H NMR (300.13 MHz, CDCl
.30 (dt, J (HH) ) 16.4 Hz, J (PH) ) 4.8 Hz, 2 H, CH
dt, J (HH) ) 16.4 Hz, J (PH) ) 5.3 Hz, 2 H, CH ), 7.45-5.55
m, 43 H, PPh , PPh , C , C ). Anal. Calcd for C58
Os‚THF: C, 60.86; H, 4.70. Found: C, 61.30; H, 4.60.
The presence of THF in the sample is clearly indicated by the
3
): δ 1.27 (s, 2 H, ÃstCCH
2
),
J (PC) ) 9.3 Hz, OstC), 166.2 (s, OstC-CHdC), 158.1 (s,
C(aryl)), 123.7 (s, OstC-CH), 145.3-128.2 (m, other aromatic
3
(
(
2
), 4.36
2
carbons), 47.0 (td, J (PC) ) 20.6, 6.0 Hz, PCP-CH
Calcd for C65 53BClF Os: C, 63.00; H, 4.31. Found: C,
62.81; H, 4.50.
Cr ysta llogr a p h ic An a lysis for OsCl(P P h
able crystals for X-ray diffraction study were grown by slow
diffusion of ether to a saturated solution of OsCl(PPh )(PCP)
in CH Cl . A red prism crystal of OsCl(PPh )(PCP) having
2
). Anal.
3
2
6
H
3
6
H
5
H
49
-
H
4 3
P
4 3
BClF P
3
)(P CP ). Suit-
1
H NMR signals of THF at 1.59 and 3.41 ppm (in CD
OsCl(dCdCHC(OH)P h )(P P h )(P CP ) (10). A mixture of
OsCl(PPh )(PCP) (0.30 g, 0.31 mmol) and 1,1-diphenylpropyn-
-ol (0.13 g, 0.65 mmol) in 50 mL of CH Cl was stirred at
2 2
Cl ).
2
3
3
3
2
2
3
1
2
2
approximate dimensions of 0.22 × 0.20 × 0.15 mm was
mounted in a glass capillary and used for X-ray structure
determination. Intensity data were collected on an Enraf-
Nonius CAD4 diffractometer using graphite-monochromated
room temperature for 30 min to give a brownish-red solution.
The solvent was evaporated to dryness under vacuum. A pale
pink solid was obtained when ether (50 mL) was added. The
solid was collected by filtration, washed with ether (50 mL)
and hexane (50 mL), and dried under vacuum overnight.
Mo KR radiation (λ ) 0.71073 Å) with ω-2θ scan (2θmax
)
48°). The data were corrected for Lorentz and polarization
3
1
1
50
Yield: 0.20 g, 56%. P{ H} NMR (121.5 MHz, C
(
6
D
6
1
): δ 6.4
effects. Absorption corrections by ψ-scan method (transmis-
d, J (PP) ) 12.6 Hz), -10.3 (t, J (PP) ) 12.6 Hz). H NMR
300.13 MHz, CD Cl ): δ 0.32 (s, 1 H, C(OH)), 0.84 (q, J (PH)
3.3 Hz, 1 H, ÃsdCdCH), 3.95 (dt, J (HH) )15.4 Hz, J (PH)
4.5 Hz, 2 H, CH ), 4.36 (dt, J (HH) ) 15.4 Hz, J (PH) ) 4.4
), 7.8-6.7 (m, 48 H, PPh , PPh , C , C ).
C{ H} NMR (75.5 MHz, CDCl ): δ 293.9 (q, J (PC) ) 8.5 Hz,
sion factors (0.591-1.000) were also applied. The structure was
solved by direct methods (SIR88)51 and refined by full-matrix
least-squares analysis on F (all non-hydrogen atoms anisotro-
(
2
2
)
)
2
pically) to give R ) 0.054, R ) 0.070 for 4439 independent
w
Hz, 2 H, CH
2
3
2
6
H
3
6
H
5
observed reflections [F > 3σ(F)]. All calculations were per-
1
3
1
52
3
formed using TeXsan crystallographic software package on
OsdC), 156.5 (d, J (PC) ) 62.1 Hz, C(aryl)), 146.3-112.6 (m,
other aromatic and olefinic carbons), 65.7 (s, C(OH)), 48.2 (td,
a Silicon-Graphics Computer.
Cr ysta llogr a p h ic An a lysis for OsCl(dCdCHP h )(P P h
(P CP )‚H O. Crystals of 6 suitable for X-ray diffraction study
were grown by slow evaporation of solvent of a saturated
solution of OsCl(dCdCHPh)(PPh )(PCP) in wet CH Cl . A
water molecule is cocrystallized with 6. A pink plate crystal
of OsCl(dCdCHPh)(PPh )(PCP)‚H O having approximate di-
3
)-
J (PC) ) 19.5, 5.1 Hz, PCP-CH
Os: C, 66.74; H, 4.65. Found: C, 66.90; H, 4.86.
OsCl (tCCHdCP h )(P CP ) (11). A 37% hydrochloric acid
solution (0.04 mL, 0.56 mmol) was added to a CH Cl (50 mL)
solution of OsCl(dCdCHC(OH)Ph )(PPh )(PCP) (0.30 g, 0.26
2
). Anal. Calcd for C65
H
54ClOP
3
-
2
2
2
3
2
2
2
2
2
3
3
2
mmol). The resulting mixture was stirred at room temperature
for 1 h to give a yellowish-green solution. The solvent was
evaporated to dryness under vacuum. A light green solid was
obtained when ether (30 mL) was added. The solid was
collected by filtration, washed with ether (2 × 30 mL), and
mensions of 0.14 × 0.10 × 0.10 mm was mounted in a glass
fiber and used for X-ray structure determination. Intensity
data were collected on a Bruker SMART CCD area detector.
The intensity data were corrected for SADABS (Siemens Area
Detector Absorption)53 (from 0.732 to 1 on I). The structure
was solved by direct methods and refined by full-matrix least-
squares analysis on F2 using the SHELXTL (version 5.10)
program package. All non-hydrogen atoms were refined aniso-
tropically. The H atoms of the solvent water molecules were
located from a difference Fourier map but not refined. The
remaining H atoms were placed in ideal positions and refined
via a riding model with assigned isotropic thermal parameters.
3
1
1
dried under vacuum overnight. Yield: 0.16 g, 75%. P{ H}
1
54
NMR (121.5 MHz, CDCl
3
): δ 14.8 (s). H NMR (300.13 MHz,
): δ 3.53 (dt, J (HH) ) 16.4 Hz, J (PH) ) 5.0 Hz, 2 H,
), 4.52 (dt, J (HH) ) 16.4 Hz, J (PH) ) 5.1 Hz, 2 H, CH ),
CD
CH
2
Cl
2
2
2
4
3
.74 (t, J (PH) ) 1.8 Hz, 1H, CH)), 6.48-8.00 (m, 48 H, PPh ,
PPh , C H , C H ). C{ H} NMR (75.5 MHz, CD Cl ): δ 275.0
2 6 3 6 5 2 2
1
3
1
(
t, J (PC) ) 11.5 Hz, OstC), 160.4 (s, C(aryl)), 154.0 (s, Ost
C-CHdC), 131.8 (s, OstC-CH), 147.3-102.2 (m, other
Ack n ow led gm en t. The authors acknowledge finan-
cial support from the Hong Kong Research Grants
Council.
aromatic carbons), 44.5 (t, J (PC) ) 19.4 Hz, PCP-CH
Calcd for C47
C, 60.65; H, 4.55; Cl, 8.29.
OsCl(tCCHdCP h )(P P h
2
). Anal.
H
38Cl
2
P
2
Os: C, 60.97; H, 4.14; Cl, 7.68. Found:
[
2
3
)(P CP )]BF
4
(12). HBF
4
(60 µL,
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic details, bond distances and angles, atomic coordi-
nates and equivalent isotropic displace coefficients, and aniso-
0
.44 mmol, 54% solution in ether) was added to a brownish-
red CH Cl solution (40 mL) of OsCl(dCdCHC(OH)Ph )(PPh )-
PCP) (0.30 g, 0.26 mmol). The reaction mixture was stirred
2
2
2
3
(
tropic displacement coefficients for OsCl(PPh
3
)(PCP) and
at room temperature for 30 min to give a brownish-orange
solution. The volume of the reaction mixture was reduced to
ca. 5 mL, and ether (30 mL) was added slowly with stirring to
give a brownish-orange solid. The crude product was collected
by filtration, washed with ether (2 × 30 mL), and dried under
vacuum overnight (0.23 g, 71.9%). The crude product was
redissolved in 20 mL of dichloromethane. After filtration, the
filtrate was concentrated in vacuo to 5 mL. Addition of ether
OsCl(dCdCHPh)(PPh )(PCP)‚H O. The material is available
3
2
free of charge via the Internet at http://pubs.acs.org.
OM000150I
(
50) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr.
968, A24, 351.
51) Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo, C.;
1
(
Polidori, G.; Spagna, R.; Viterbo, D. J . Appl. Crystallogr. 1989, 22, 389.
(52) Texan, Crystal Structure Analysis Package; Molecular Structure
Corporation: 1985 and 1982.
(20 mL) to the residue produced a brownish-orange solid,
which was collected by filtration, washed with ether (3 × 30
(
53) Sheldrick, G. M. SADABS, Absorption Correction Program;
University of G o¨ ttingen: Germany, 1996.
54) SHELXTL Reference Manual (Version 5.1); Bruker Analytical
X-ray Systems Inc.; Madison, WI, 1997.
mL), and dried under vacuum overnight to give 0.18 g (yield,
1
5
(
6.2%) of product. 31P{ H} NMR (121.5 MHz, CDCl
3
1
): δ 10.5
(
d, J (PP) ) 12.6 Hz), -19.3 (t, J (PP) ) 12.6 Hz). H NMR