Synthesis and characterization of trimetallic ruthenium and bimetallic osmium complexes with metal-vinyl linkages

Article abstract of DOI:10.1021/om0496939

Treatment of RuHCl(CO)(PPh₃)₃ with 1,3,5-triethynylbenzene produces the trimetallic complex 1,3,5-[Cl(CO)(PPh ₃)₂RuCH=CH]₃C₆H₃, which reacts with PMe₃ to give 1,3,5-[C

Full text of DOI:10.1021/om0496939

562
Organometallics 2005, 24, 562-569
Synthesis and Characterization of Trimetallic
Ruthenium and Bimetallic Osmium Complexes with
Metal-Vinyl Linkages
Haiping Xia,† Ting Bin Wen,† Quan Yuan Hu,† Xin Wang,† Xingguo Chen,†
Lai Yung Shek,† Ian D. Williams,† Kam Sing Wong,*,‡ George K. L. Wong,*,‡ and
Guochen Jia*,†
Department of Chemistry and Open Laboratory of Chirotechnology of the Institute of
Molecular Technology for Drug Discovery and Synthesis and Department of Physics,
The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Received May 2, 2004
Treatment of RuHCl(CO)(PPh3)3 with 1,3,5-triethynylbenzene produces the trimetallic
complex 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3, which reacts with PMe3 to give 1,3,5-[Cl-
(CO)(PMe3)3RuCHdCH]3C6H3. 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3 also reacts with py-
ridine (Py) and 4-phenylpyridine (PhPy) to give 1,3,5-[Cl(CO)(L)(PPh3)2RuCHdCH]3C6H3
(L ) Py, PhPy). Reactions of OsHCl(CO)(PPh3)3 with ArCtCH (Ar ) Ph, p-tolyl) produce
the six-coordinated insertion products OsCl(CHdCHAr)(CO)(PPh3)3. Reaction of OsHCl(CO)-
(PPh3)3 with 1,3,5-triethynylbenzene produces the bimetallic complex 1-HCtC-3,5-[Cl(CO)-
(PPh3)3OsCHdCH]2C6H3, which reacts with PMe3 to give 1-HCtC-3,5-[OsCl(CO)(PPh3)2-
(PMe3)OsCHdCH]2C6H3. The electrochemical and second-order NLO properties of some of
the new complexes have been investigated.
Introduction
C]3C6H3 (M ) Ru,6a,7 Os2b), 1,3,5-[(P(i-Pr)3)2ClRhdCd
CH]3C6H3,8 {1,3,5-[(dppe)2ClRudCdCHC6H4CtC]3C6H3}-
(PF6)3,7 1,3,5-[(4-C6H3(3,5-CH2NMe2)2)ClPd]3C6H3,15 and
Hyperbranched and dendritic organometallic com-
pounds with metal centers linked by conjugated bridges
are attracting considerable attention because of their
material and catalytic properties.1 A number of such
complexes, either trimetallic or polymetallic in nature,
have been synthesized in recent years, especially for
those with a 1,3,5-substituted benzene core.2-16 Most
of the reported complexes have M-CtC,2b,c,3-14 MdCd
CHR,2d,7,8 M-aryl,15 or M-L (L ) η2-RCtCR′,2a,f,16a-c
η6-arene,16e N,2g,16f-g or P16h donors) linkages, for ex-
ample, 1,3,5-[LnMCtC]3C6H3 (M ) Fe,3 Ru,5 Rh,8 Ir,9
Pd,10,11 Pt,11-13 and Au14), 1,3,5-[LnMCtCC6H4Ct
(6) (a) McDonagh, A. M.; Humphrey, M. G.; Samoc, M.; Luther-
Davies, B.; Houbrechts, S.; Wada, T.; Sasabe, H.; Persoons, A. J. Am.
Chem. Soc. 1999, 121, 1405. (b) McDonagh, A. M.; Humphrey, M. G.;
Samoc, M.; Luther-Davies, B. Organometallics 1999, 18, 5195. (c)
Hurst, S. K.; Humphrey, M. G.; Isoshima, T.; Wostyn, K.; Asselberghs,
I.; Clays, K.; Persoons, A.; Samoc, M.; Luther-Davies, B. Organome-
tallics 2002, 21, 2024. (d) Hurst, S. K.; Cifuentes, M. P.; Humphrey,
M. G. Organometallics 2002, 21, 2353.
(7) Uno, M.; Dixneuf, P. H. Angew. Chem., Int. Ed. 1998, 37, 1714.
(8) Werner, H.; Bachmann, P.; Laubender, M.; Gevert, O. Eur. J.
Inorg. Chem. 1998, 1217.
(9) Tykwinski, R. R.; Stang, P. J. Organometallics 1994, 13, 3203.
(10) Yam, V. W. W.; Zhang, L.; Tao, C. H.; Wong, K. M. C.; Cheung,
K. K. J. Chem. Soc., Dalton Trans. 2001, 1111.
† Department of Chemistry and Open Laboratory of Chirotechnology
of the Institute of Molecular Technology for Drug Discovery and
Synthesis.
(11) Yam, V. W. W.; Tao, C. H.; Zhang, L.; Wong, K. M. C.; Cheung,
K. K. Organometallics 2001, 20, 453.
(12) Leininger, S.; Stang, P. J.; Huang, S. Organometallics 1998,
17, 3981.
‡ Department of Physics.
(1) Oosterom, G. E.; Beck, J. N. H.; Kamer, P. C.; van Leeuwen, P.
W. N. M. Angew. Chem., Int. Engl. 2001, 40, 1828. (b) Long, N. J.;
Williams, C. K. Angew. Chem. Int. Ed. 2003, 42, 2586.
(2) Examples of recent work, see: (a) Lucas, N. T.; Notaras, E. G.
A.; Cifuentes, M. P.; Humphrey, M. G. Organometallics 2003, 22, 284.
(b) Morrall, J. P.; Powell, C. E.; Stranger, R.; Cifuentes, M. P.;
Humphrey, M. G.; Heath, G. A. J. Organomet. Chem. 2003, 670, 248.
(c) McDonagh, A. M.; Powell, C. E.; Morrall, J. P.; Cifuentes, M. P.;
Humphrey, M. G. Organometallics 2003, 22, 1402. (d) Weiss, D.;
Dixneuf, P. H. Organometallics 2003, 22, 2209. (e) Huang, C. H.; Lin,
Y. C.; Huang, S. L.; Liu, Y. H.; Wang, Y. Organometallics 2003, 22,
1512. (f) Yao, H.; Sabat, M.; Grimes, P. N.; Zanello, P.; Febrizia, de
Biani, F. Organometallics 2003, 22, 2581. (g) Liu, Q. D.; Jia, W. L.;
Wu, G.; Wang, S. Organometallics 2003, 22, 3781.
(3) (a) Weyland, T.; Costuas, K.; Toupet, L.; Halet, J. F.; Lapinte,
C. Organometallics 2000, 19, 4228. (b) Weyland, T.; Costuas, K.; Mari,
A.; Halet, J. F.; Lapinte, C. Organometallics 1998, 17, 5569. (c)
Weyland, T.; Lapinte, C.; Frapper, G.; Calhorda, M. J.; Halet, J. F.;
Toupet, L. Organometallics 1997, 16, 2024.
(4) Long, N. J.; Martin, A. J.; de Biani, F. F.; Zanello, F. J. Chem.
Soc., Dalton Trans. 1998, 2017.
(5) Long, N. J.; Martin, A. J.; White, A. J. P.; Williams, D. J.;
Fontani, M.; Laschi, F.; Zanello, P. J. Chem. Soc., Dalton Trans. 2000,
3387.
(13) (a) Ohshiro, N.; Takei, F.; Onitsuka, K.; Takahashi, S. J.
Organomet. Chem. 1998, 569, 195. (b) Onitsuka, K.; Fujimoto, M.;
Ohshiro, N.; Takahashi, S. Angew. Chem., Int. Ed. 1999, 38, 689.
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544, 277. (b) Irwin, M. J.; Manojlovic-Muir, L.; Muir, K. W.; Pud-
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metallics 2001, 20, 3159.
(16) For additional work, see for example: (a) Moreno, C.; Marcos,
M. L.; Dominguez, G.; Arnanz, A.; Farrar, D. H.; Teeple, R.; Lough,
A.; Gonza´lez-Velasco, J.; Delgado, S. J. Organomet. Chem. 2001, 631,
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Byrne, J. J.; Long, C. J. Organomet. Chem. 1999, 589, 157. (c) Pellny,
P. M.; Burlakov, V. V.; Baumann, W.; Spannenberg, A.; Kempe, R.;
Rosenthal, U. Organometallics 1999, 18, 2906. (d) Fink, H.; Long, N.
J.; Martin, A. J.; Opromolla, G.; White, A. J. P.; Williams, D. J.; Zanello,
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Chem. Ber. 1996, 129, 604. (f) Stang, P. J.; Olenyuk, B.; Muddiman,
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18, 2565.
10.1021/om0496939 CCC: $30.25 © 2005 American Chemical Society
Publication on Web 01/13/2005

Trimetallic Ru and Bimetallic Os Complexes
Organometallics, Vol. 24, No. 4, 2005 563
1,3,5-[(Co2(CO)6)(HtC-)]3C6H3.16a These complexes can
have interesting physical properties. For example,
complexes such as 1,3,5-[Cl(PEt3)2MCtCC6H4CtC]3C6H3
(M ) Pd, Pt) exhibit luminescent properties,10,11 com-
plexes such as 1,3,5-[(PPh3)AuCtC]3C6H3,14a 1,3,5-[Cl-
(dppe)2RuCtCC6H4CtC]3C6H3,6a and 1,3,5-[Cl(dppm)2-
Scheme 1
6c
RuCtCC6H4CHdCH]3C6H3 have good NLO proper-
ties, and complexes such as 1,3,5-[Cp*(dppe)FeCt
C]3C6H33 and [Cp(PPh3)2RuCtC]3C6H34 show electronic
cooperation between individual metal centers.
Although a number of trimetallic acetylide complexes
of the type 1,3,5-[LnMCtC]3C6H3 have been re-
ported,3,5-14 the related vinyl complexes 1,3,5-[LnMCHd
CH]3C6H3 are still unknown. These vinyl complexes are
interesting especially in view of the fact that tris(vinyl)-
benzenes,17 1,3,5-[LnMCtC]3C6H3, and related com-
plexes show NLO and interesting electrochemical prop-
erties. In this report, we wish to report the synthesis
and characterization of trimetallic ruthenium vinyl
complexes of the type 1,3,5-[LnRuCHdCH]3C6H3.
Results and Discussion
Synthesis and Characterization of 1,3,5-[Cl(CO)-
(PPh3)2RuCHdCH]3C6H3 and Related Compounds.
Reactions of RuHCl(CO)(PPh3)3 (1) with HCtCR have
been shown to readily give RuCl((E)-CHdCHR)(CO)-
(PPh3)2.18,19 The reaction has been used previously to
prepare bimetallic complexes such as [RuCl(CO)(PPh3)2]2-
(µ-CHdCH-Ar-CHdCH)20 and [RuCl(CO)(PPh3)2]2(µ-
(CHdCH)n) (n ) 2, 3, 4).21 Thus it is expected that
reaction of 1 with 1,3,5-triethynylbenzene (2) will
produce the trimetallic complex 1,3,5-[Cl(CO)(PPh3)2-
RuCHdCH]3C6H3. Indeed, addition of 2 to a suspension
of RuHCl(CO)(PPh3)3 (1) in dichloromethane rapidly
produced 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3 (3),
which can be isolated as an orange-red solid in 92% yield
(Scheme 1).
with a 3J(HH) coupling constant of 13.2 Hz. The
magnitude of the coupling constant indicates that the
two vinylic protons are in trans geometry and that the
acetylene is cis inserted into the Ru-H bond. The core
C6H3 proton signal was observed at 6.72 ppm in the 1H
NMR spectrum. In the 13C{1H} NMR spectrum (in
C6D6), the RuCH signal and the RuCHdCH signal were
observed at 146.7 and 137.2 ppm, respectively. Mono-
meric complexes RuCl(RCdCHR′)(CO)(PPh3)2 are known
to adopt a distorted trigonal bipyramidal geometry
around ruthenium with the two PPh3 ligands in the
apical positions.19 Thus it is assumed that complex 3
has a similar geometry around ruthenium. [RuCl(CO)-
22
(PPh3)2(CHdCH)]3B3N3Me3 is a reported trimetallic
complex structurally related to 3.
Compound 3 has been characterized by NMR and
elemental analysis. The 31P{1H} NMR spectrum in C6D6
showed a singlet at 29.9 ppm, the chemical shift of
which is typical for RuCl((E)-CHdCHR)(CO)(PPh3)2.21
Three new trimetallic complexes were prepared from
complex 3. Treatment of 3 with PMe3 produced the six-
coordinated complex 1,3,5-[Cl(CO)(PMe3)3RuCHdCH]3-
C6H3 (4) (Scheme 1). The PMe3 ligands in 4 are meridi-
onally coordinated to ruthenium as indicated by the
AM2 pattern 31P{1H} NMR spectrum. The presence of
1
The H NMR spectrum in CD2Cl2 displayed the RuCH
signal at 8.84 ppm and the â-CH signal at 6.20 ppm
(17) (a) Cho, B. R.; Lee, S. J.; Lee, S. H.; Son, K. K.; Kim, Y. H.;
Doo, J. Y.; Lee, G. J.; Kang, T. I.; Lee, Y. K.; Cho, M.; Jeon, S. J. Chem.
Mater. 2001, 13, 1438. (b) Cho, B. R.; Park, S. P.; Lee, S. J.; Son, K.
K.; Lee, S. H.; Lee, M. J.; Yoo, J.; Lee, Y. K.; Lee, G. J.; Kang, T. I.;
Cho, M.; Jeon, S. J. J. Am. Chem. Soc. 2001, 123, 6421.
(18) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J. J. Organomet. Chem.
1986, 309, 169.
(19) For recent work, see for example: (a) Maruyama, Y.; Yama-
mura, K.; Sagawa, T.; Katayama, H.; Ozawa, F. Organometallics 2000,
19, 1308. (b) Maruyama, Y.; Yamamura, K.; Nakayama, I.; Yoshiuchi,
K.; Ozawa, F. J. Am. Chem. Soc. 1998, 120, 1421. (c) Harlow, K. J.;
Hill, A. F.; Welton, T. J. Chem. Soc., Dalton Trans. 1999, 1911. (d)
Hill, A. F.; Ho, C. T.; Wilton-Ely, J. D. E. T. Chem. Commun. 1997,
2207. (e) Harlow, K. J.; Hill, A. F.; Welton, T.; White, A. J. P.; Williams,
D. J. Organometallics 1998, 17, 1916. (f) Jia, G.; Wu, W. F.; Yeung, R.
C. Y.; Xia, H. J. Organomet. Chem. 1997, 538, 31.
(20) (a) Go´mez-Lor, B.; Santos, A.; Ruiz, M.; Echavarren, A. M. Eur.
J. Inorg. Chem. 2001, 2305. (b) Jia, G.; Wu, W. F.; Yeung, R. C. Y.;
Xia, H. P. J. Organomet. Chem. 1997, 539, 53. (c) Santos, A.; Lo´pez,
J.; Montoya, J.; Noheda, P.; Romero, A.; Echavarren, A. M. Organo-
metallics 1994, 13, 3605.
1
the 1,3,5-(CHdCH)3C6H3 unit is indicated by the H
NMR spectrum (in acetone-d6), which showed the
RuCHdCH proton signals at 8.13 (RuCH) and 6.65 (â-
CH) ppm and the C6H3 signal at 7.02 ppm. In addition,
the 13C{1H} NMR spectrum (in CD2Cl2) showed three
CH signals at 163.0 (RuCH), 135.9 (â-CH), and 117.3
(C6H3) ppm. The vinyl group is trans to the unique PMe3
ligand, as indicated by the large 2J(PC)trans coupling
constant (76.9 Hz).
Reactions of 3 with pyridine (Py) and 4-phenylpyri-
dine (PhPy) gave the corresponding six-coordinated
complexes [Cl(Py)(CO)(PPh3)2RuCHdCH]3C6H3 (5) and
[Cl(PhPy)(CO)(PPh3)2RuCHdCH]3C6H3 (6), respectively.
Related mononuclear complexes RuCl(CHdCHR)(L)-
(CO)(PPh3)2 (L ) 2e nitrogen donor ligands) have been
previously prepared from the reactions of HCtCR with
RuHCl(L)(CO)(PPh3)2.23 In contrast, complex 3 does not
react with PPh3 to give the corresponding six-coordi-
nated complex, due to the steric bulkiness.
(21) (a) Xia, H. P.; Jia, G. Organometallics 1997, 16, 1. (b) Xia, H.
P.; Yeung, R. C. Y.; Jia, G. Organometallics 1997, 16, 3557. (c) Xia, H.
P.; Yeung, R. C. Y.; Jia, G. Organometallics 1998, 17, 4762. (d) Liu, S.
H.; Chen, Y.; Wan, K. L.; Wen, T. B.; Zhou, Z.; Lo, M. F.; Williams, I.
D.; Jia, G. Organometallics 2002, 21, 4984. (e) Liu, S. H.; Xia, H. P.;
Wen, T. B.; Zhou, Z.; Jia, G. Organometallics 2003, 22, 737.

564 Organometallics, Vol. 24, No. 4, 2005
Xia et al.
are related by a pseudo-C3 rotation axis. The carbon
atoms of (CHdCH)3C6H3 are nearly coplanar, with the
dihedral angles between the core benzene ring and the
three vinyl groups at 13.3°, 15.0°, and 15.0°. The
geometry around each ruthenium center can be de-
scribed as a distorted octahedron with two mutually
trans disposed PPh3 ligands. The vinyl group is trans
to the pyridine ligand, and the chloride is trans to the
CO, as suggested by the solution NMR data. The
mutually trans PPh3 ligands are bent away from the
pyridine ligands but toward the vinyl ligands. The
Ru-C and C(R)-C(â) bond distances of complex 5 are
within the range of those reported for other ruthenium
vinyl complexes.24 In complexes such as [RuCl(CO)-
(PEt3)3]2(µ-CHdCHCHdCH)21b and [RuCl(CO)(PMe3)3]2-
(µ-CHdCHCHdCHCHdCHCHdCH),21d the vinyl groups
are essentially coplanar with Ru-CO.25 However, simi-
lar coplanarity was not observed for complex 5.
Reactions of Terminal Alkynes with OsHCl(CO)-
(PPh3)3. We were also interested in preparing analo-
gous trimetallic osmium complexes using similar chem-
istry starting from OsHCl(CO)(PPh3)3. To test the
feasibility of using OsHCl(CO)(PPh3)3 as the starting
material to prepare trimetallic osmium complexes analo-
gous to 3-6, we have studied the reactions of OsHCl-
(CO)(PPh3)3 with PhCtCH and HCtC(p-tolyl).
Figure 1. Molecular structure of 1,3,5-[Cl(CO)(Py)(PPh3)2-
RuCHdCH]3C6H3 (5). The phenyl rings and the H atoms
of pyridine are omitted for clarity.
Table 1. Crystal Data and Structure Refinement
for Complexes
1,3,5-[Cl(CO)(Py)(PPh3)2RuCHdCH]3C6H3‚CH2Cl2
(5‚CH2Cl2) and
OsCl(CHdCH(p-tolyl))(CO)(PPh3)3‚2CH2Cl2
(8b‚2CH2Cl2)
Although insertion reactions of alkynes with osmium
hydride complexes such as OsHCl(CO)(PR3)2 (PR3 ) P(i-
Pr)3,26 P(t-Bu)2Me26c), OsH(O2CCF3)(CO)(PPh3),27 and
OsHCl(CO)((BTD)(PPh3)2 (BTD ) 2,1,3-benzothiadi-
azole)28 are known, the insertion reactions of alkynes
with OsHCl(CO)(PPh3)3 have not been well studied.
While insertion reaction of OsHCl(CO)(PPh3)3 with
HCtCCH(OH)Ph2 apparently occurred in the formation
of OsCl2(dCHCHdCPh2)(CO)(PPh3)2 from the reaction
of OsHCl(CO)(PPh3)3 with HCtCCH(OH)Ph2 and Cl2-
PPh3,29 it has been briefly mentioned previously that
the insertion product from the reaction of OsHCl(CO)-
(PPh3)3 with phenylacetylene could not be obtained.28
However, we now found that OsHCl(CO)(PPh3)3 does
undergo insertion reactions with PhCtCH and HCt
C(p-tolyl).
5‚CH2Cl2
8b‚2CH2Cl2
empirical formula
C
139H116Cl5N3O3P6Ru3
C
66H58Cl5OOsP3
fw
2542.63
294(2)
0.71073
1327.48
100(2)
temperature, K
radiation (Mo Ka),
Å
0.71073
cryst syst
space group
a, Å
monoclinic
P21/c
orthorhombic
Pbca
18.9198(10)
24.2415(12)
24.7661(12)
22.6945(2)
19.0662(2)
30.4423(2)
105.5780(10)
12688.44(17)
4
b, Å
c, Å
â, deg
volume, Å3
Z
11358.8(10)
8
density(calcd),
1.331
1.533
g cm-3
absorp coeff, mm-1 0.586
2.609
5344
0.20 × 0.15 × 0.12
1.59 to 26.00
85 130
F(000)
5208
cryst size, mm3
θ range, deg
no. of reflns
collected
0.50 × 0.45 × 0.38
1.27 to 25.08
48 046
Addition of PhCtCH to a solution of OsHCl(CO)-
(PPh3)3 (7) in dichloromethane produced an orange
no. of indep reflns
22 423 [R(int) )
0.0682]
11 096 [R(int) )
0.1870]
6510
(22) Hu, Q. Y.; Lo, M. F.; Williams, I. D.; Koda, N.; Uchimarum, Y.;
Lo, M. F.; Williams, I. D.; Jia, G. J. Organomet. Chem. 2003, 670, 243.
(23) (a) Santos, A.; Lo´pez, J.; Gala´n, A.; Gonza´lez, J. J.; Tinoco, P.;
Echavarren, A. M. Organometallics 1997, 16, 3482. (b) Romereo, A.;
Santos, A.; Lo´pez, J.; Echavarren, A. M. J. Organomet. Chem. 1990,
391, 219.
no. of obsd reflns
[I>2σ(I)]
absorp corr
max. and min.
transmn
11 791
SADABS
1.000 and 0.7316
SADABS
1.000 and 0.8534
(24) See for example: (a) Torres, M. R.; Santos, A.; Perales, A.; Ros,
J. J. Organomet. Chem. 1988, 353, 221. (b) Romero, A.; Santos, A.;
Vegas, A. Organometallics 1988, 7, 1988. (c) Lo´pez, J.; Romero, A.;
Santos, A.; Vegas, A.; Echavarren, A. M.; Noheda, P. J. Organomet.
Chem. 1989, 373, 249. (d) Alcock, N. W.; Hill, A. F.; Melling, R. P.
Organometallics 1991, 10, 3898. (e) Wakatsuki, Y.; Yamazaki, H.;
Kumegawa, N.; Satoh, T.; Satoh, J. Y. J. Am. Chem. Soc. 1991, 113,
9604.
no. of data/
restraints/
params
22 423/78/1432
11 096/6/685
goodness-of-fit on F2 1.069
0.828
final R indices
[I>2σ(I)]
R1 ) 0.0721,
wR2 ) 0.1622
0.931/-0.447
R1 ) 0.0524,
wR2 ) 0.1012
1.032/-0.902
largest diff peak/
(25) Choi, S. H.; Bytheway, I.; Lin, Z.; Jia, G. Organometallics 1998,
17, 3974.
hole, e Å-3
(26) (a) Marchenko, A. V.; Gerard, H.; Eisenstein, O.; Caulton, K.
G. New. J. Chem. 2001, 25, 1244. (b) Esteruelas, M. A.; Oro, L. A.;
Valero, C. Organometallics 1995, 14, 3596. (c) Werner, H.; Meyer, U.;
Peters, K.; von Schnering, H. G. Chem. Ber. 1989, 122, 2097. (d)
Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986, 5, 2295.
(27) Dobson, A.; Moore, D. S.; Robinson, S. D.; Hursthouse, M. B.;
New, L. Polyhedron 1985, 4, 1119.
The structure of 5 has been confirmed by X-ray
diffraction, and its molecular structure is depicted in
Figure 1. The crystallographic details and selected bond
distances and angles are given in Tables 1 and 2,
respectively. As shown in Figure 1, the compound
contains three ruthenium centers linked by a 1,3,5-
(CHdCH)3C6H3 bridge. The three ruthenium centers
(28) Hill, A. F.; Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans.
1998, 3501.
(29) Harlow, K. J.; Hill, A. F.; Welton, T. J. Chem. Soc., Dalton
Trans. 1999, 1911.

Trimetallic Ru and Bimetallic Os Complexes
Organometallics, Vol. 24, No. 4, 2005 565
Table 2. Selected Bond Distances and Angles for 1,3,5-[Cl(CO)(Py)(PPh3)2RuCHdCH]3C6H3 (5)
Bond Distances (Å)
Ru(1)-P(1)
Ru(1)-P(2)
Ru(1)-Cl(1)
Ru(1)-C(1)
Ru(1)-C(11)
Ru(1)-N(1)
C(1)-O(1)
2.397(2)
2.389(2)
2.475(2)
1.809(10)
2.050(8)
2.276(7)
1.105(10)
1.326(10)
Ru(2)-P(4)
Ru(2)-P(3)
Ru(2)-Cl(2)
Ru(2)-C(2)
Ru(2)-C(21)
Ru(2)-N(2)
C(2)-O(2)
2.395(2)
2.389(2)
2.454(2)
1.814(9)
2.043(7)
2.271(7)
1.145(9)
1.311(9)
Ru(3)-P(5)
Ru(3)-P(6)
Ru(3)-Cl(3)
Ru(3)-C(3)
Ru(3)-C(31)
Ru(3)-N(3)
C(3)-O(3)
2.404(2)
2.404(2)
2.474(2)
1.806(10)
2.038(7)
2.243(7)
1.167(10)
1.330(10)
C(11)-C(12)
C(21)-C(22)
C(31)-C(32)
Bond Angles (deg)
P(2)-Ru(1)-P(1)
C(11)-Ru(1)-N(1)
C(1)-Ru(1)-N(1)
C(11)-Ru(1)-P(1)
C(11)-Ru(1)-P(2)
N(1)-Ru(1)-P(2)
P(2)-Ru(1)-Cl(1)
N(1)-Ru(1)-Cl(1)
P(3)-Ru(2)-P(4)
C(21)-Ru(2)-N(2)
C(2)-Ru(2)-N(2)
C(21)-Ru(2)-P(3)
N(2)-Ru(2)-P(4)
N(2)-Ru(2)-P(3)
P(4)-Ru(2)-Cl(2)
N(2)-Ru(2)-Cl(2)
P(6)-Ru(3)-P(5)
C(31)-Ru(3)-N(3)
C(3)-Ru(3)-N(3)
C(31)-Ru(3)-P(5)
N(3)-Ru(3)-P(6)
N(3)-Ru(3)-P(5)
P(6)-Ru(3)-Cl(3)
N(3)-Ru(3)-Cl(3)
C(02)-C(01)-C(12)
C(02)-C(03)-C(22)
C(04)-C(05)-C(32)
C(11)-C(12)-C(01)
C(21)-C(22)-C(03)
C(31)-C(32)-C(05)
172.18(8)
174.2(3)
93.5(3)
C(1)-Ru(1)-Cl(1)
178.2(3)
C(1)-Ru(1)-C(11)
C(1)-Ru(1)-P(1)
91.9(4)
90.4(3)
85.5(2)
C(1)-Ru(1)-P(2)
91.8(3)
86.9(2)
N(1)-Ru(1)-P(1)
P(1)-Ru(1)-Cl(1)
C(11)-Ru(1)-Cl(1)
O(1)-C(1)-Ru(1)
C(2)-Ru(2)-Cl(2)
C(2)-Ru(2)-C(21)
C(2)-Ru(2)-P(3)
96.43(19)
91.35(9)
87.8(2)
90.90(19)
86.34(8)
86.7(2)
178.6(10)
179.7(3)
91.9(3)
169.78(8)
175.8(3)
92.3(3)
86.8(2)
96.5(2)
93.05(19)
87.63(7)
87.6(2)
90.5(2)
C(2)-Ru(2)-P(4)
92.7(2)
C(21)-Ru(2)-P(4)
P(3)-Ru(2)-Cl(2)
C(21)-Ru(2)-Cl(2)
O(2)-C(2)-Ru(2)
C(3)-Ru(3)-Cl(3)
C(3)-Ru(3)-C(31)
C(3)-Ru(3)-P(5)
C(3)-Ru(3)-P(6)
C(31)-Ru(3)-P(6)
P(5)-Ru(3)-Cl(3)
C(31)-Ru(3)-Cl(3)
O(3)-C(3)-Ru(3)
C(06)-C(01)-C(12)
C(04)-C(03)-C(22)
C(06)-C(05)-C(32)
C(12)-C(11)-Ru(1)
C(22)-C(21)-Ru(2)
C(32)-C(31)-Ru(3)
83.4(2)
89.16(8)
88.2(2)
177.4(8)
177.0(3)
91.0(3)
172.09(8)
173.4(3)
95.4(3)
90.1(3)
83.4(2)
90.4(3)
92.6(2)
88.7(2)
95.2(2)
92.59(8)
87.8(2)
86.75(8)
85.8(2)
178.2(7)
123.2(7)
119.3(7)
120.4(7)
134.5(6)
134.4(6)
136.5(6)
118.9(6)
123.1(7)
122.3(7)
127.3(7)
126.7(7)
123.8(7)
solution, from which the six-coordinated insertion prod-
uct OsCl(CHdCHPh)(CO)(PPh3)3 (8a) can be isolated
as a light pink solid in 71% yield (eq 1). The insertion
reaction is different from the reaction of HCtCPh with
RuHCl(CO)(PPh3)3 in that the latter reaction gives the
five-coordinated complex RuCl(CHdCHPh)(CO)(PPh3)2.18
Compound 8a has been characterized by NMR and
elemental analysis. The 31P{1H} NMR spectrum in
CDCl3 at room temperature showed two broad signals
at -11.6 and -22.7 ppm, indicating that the compound
is fluxional. In toluene-d8 at 203 K, the fluxional process
is slowed and the 31P{1H} NMR spectrum showed a
doublet at -11.6 ppm and a triplet at -24.6 ppm with
a coupling constant of 12.1 Hz. The NMR data clearly
indicate that compound 8a has three PPh3 ligands
meridionally coordinated to osmium. The presence of the
Figure 2. Molecular structure of [OsCl(CHdCH(p-tolyl)-
(CO)(PPh3)3 (8b).
insertion product OsCl(CHdCH(p-tolyl))(CO)(PPh3)3 (8b).
The spectroscopic data of 8b are similar to that of 8a,
indicating that they have similar structures.
The structure of 8b has been confirmed by X-ray
diffraction. The molecular structure of 8b is depicted
in Figure 2. The crystallographic details and selected
bond distances and angles are given in Tables 1 and 3,
respectively. As shown in Figure 2, the compound
contains three meridionally bound PPh3 ligands and a
1
vinyl ligand is supported by the H NMR spectrum (in
toluene-d8 at 203 K), which displayed the OsCH signal
at 8.32 ppm. In addition, the 13C{1H} NMR spectrum
showed OsCHdCH signals at 147.7 and 135.5 ppm,
respectively. Under similar conditions, reaction of HCt
C(p-tolyl) with OsHCl(CO)(PPh3)3 gave the analogous

566 Organometallics, Vol. 24, No. 4, 2005
Table 3. Selected Bond Distances and Angles for OsCl(CHdCH(p-tolyl))(CO)(PPh3)3 (8b)
Xia et al.
Bond Distances (Å)
Os(1)-C(10)
Os(1)-P(2)
C(1)-C(2)
1.837(7)
2.4386(19)
1.366(10)
Os(1)-C(1)
2.105(7)
Os(1)-P(1)
Os(1)-P(3)
C(10)-O(1)
2.4041(19)
2.500(19)
1.146(8)
Os(1)-Cl(1)
C(2)-C(3)
2.4772(16)
1.464(10)
Bond Angles (deg)
C(10)-Os(1)-C(1)
86.9(3)
C(10)-Os(1)-P(1)
91.3(2)
C(10)-Os(1)-P(2)
C(10)-Os(2)-Cl(1)
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)
Os(1)-C(10)-O(1)
95.6(2)
172.8(2)
83.28(18)
85.9(2)
97.59(6)
95.77(6)
101.30(6)
176.0(6)
C(10)-Os(1)-P(3)
C(1)-Os(1)-P(1)
C(1)-Os(1)-P(3)
P(1)-Os(1)-P(3)
P(1)-Os(1)-Cl(1)
P(2)-Os(1)-Cl(1)
Os(1)-C(1)-C(2)
85.9(2))
84.23(8)
172.61(9)
165.36(7)
88.53(6)
83.00(6)
130.6)
Table 4. Electrochemical Data for Compounds
Scheme 2
3-6a
compound
Epa, V
Epc, V
E1/2, V
∆Ep, mV
3
4
5
0.98b
0.76b
0.60
1.01
1.28
0.58
0.96
1.16
0.48
0.82
1.08
0.49
0.84
1.03
0.54
0.92
1.19
0.54
0.94
1.10
120
190
200
90
120
130
6
a All data were obtained in CH2Cl2 containing 0.10 M n-Bu4NClO4
as the supporting electrolyte with a scan rate of 100 mV/s, E1/2
(Epa + Epc)/2, ∆Ep ) Epa - Epc
b Irreversible oxidation peak.
)
.
vinyl ligand trans to the unique PPh3 ligand. The Os-
C(1) and C(1)-C(2) bond distances are normal compared
to those reported for other osmium vinyl complexes.30
Synthesis and Characterization of 1-HCtC-3,5-
[Cl(CO)(PPh3)3OsCHdCH]2C6H3 and Related Com-
pounds. Treatment of OsHCl(CO)(PPh3)3 (7) with 1,3,5-
triethynylbenzene in dichloromethane produced the
bimetallic complex 1-HCtC-3,5-[Cl(CO)(PPh3)3OsCHd
CH]2C6H3 (9) (Scheme 2). The expected trimetallic
complex could not be obtained, however, even when
more than 3 equiv of OsHCl(CO)(PPh3)3 was used.
Compound 9 has been characterized by NMR and
elemental analysis. The 31P{1H} NMR data are similar
to those of 8. The 1H NMR spectrum in C6D6 displayed
the OsCH signal at 7.85 ppm, the OsCHdCH signal at
6.07 ppm, and the two C6H3 signals at 6.37 and 6.79
ppm. Reported bimetallic complexes closely related to
9 include [MCl(P(i-Pr)3)2]CHdCH(CH2)4CHdCH[MCl-
(P(i-Pr)3)2] (M ) Ru, Os) and [RuCl(P(i-Pr)3)2]CHdCH-
(CH2)4CHdCH[OsCl(P(i-Pr)3)2].31
It is interesting to note that the reaction of 1,3,5-
(HCtC)3C6H3 with OsHCl(CO)(PPh3)3 gives the bime-
tallic complex 9, but the reaction of 1,3,5-(HCtC)3C6H3
with RuHCl(CO)(PPh3)3 produces the trimetallic com-
plex 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3. Probably,
the presence of three bulky PPh3 ligands in the osmium
centers of 9 prevents the further insertion reaction of 9
with OsHCl(CO)(PPh3)3 to give a trimetallic complex.
Complex 9 also failed to react with 1 to give a trimetallic
complex. We have tried to replace the PPh3 ligands with
PMe3, to reduce the steric effect. Reaction of 9
with PMe3 produced 1-HCtC-3,5-[Cl(CO)(PPh3)2(PMe3)-
OsCHdCH]2C6H3 (10). The PPh3 ligands cannot be
completely exchanged with PMe3, even when excess
PMe3 was used. As expected, complex 10 also failed to
react with OsHCl(CO)(PPh3)3.
Electrochemistry. Electrochemistry has often be
used to assess the electronic communication of metal
centers in bi- and polymetallic complexes. The redox
behavior of trimetallic complexes 3-6 in CH2Cl2 have
been investigated by cyclic voltammetry with n-Bu4-
NClO4 as the supporting electrolyte, and the results are
collected in Table 4.
Three oxidation waves are expected for the trimetallic
complexes if the metal centers interact with each other
electronically. The three oxidation waves were resolved
for complexes 5 and 6. As an illustration, the cyclic
voltammogram of complex 5 is shown in Figure 3. As
can be seen from Figure 3, the cyclic votammogram of
complex 5 showed three oxidation waves at 0.54, 0.92,
and 1.19 V vs Ag/AgCl, which can be tentatively
attributed to the formation of 5+(Ru(II)/Ru(II)/Ru(III)),
5
2+(Ru(II)/Ru(III)/Ru(III)), and 53+(Ru(III)/Ru(III)/Ru-
(III)), respectively. The peak separation between the
first and the second oxidation waves and that between
the second and the third oxidation waves are at 0.38
and 0.27 V, respectively. Similarly, complex 6 exhibited
three oxidation waves at 0.54, 0.90, and 1.10 V vs Ag/
AgCl with peak separations of 0.36 and 0.20 V. The
appreciable peak separations in the oxidation of com-
plexes 5 and 6 indicate that there exist appreciable
interactions between the metal centers. Interestingly,
the peak separations between the first and the second
oxidation waves of 5 and 6 are larger than those
between the second and the third oxidation waves.
(30) (a) Wen, T. B.; Zhou, Z. Y.; Jia, G. Organometallics 2003, 22,
4947. (b) Castarlenas, R.; Esteruelas, M. A.; On˜ate, E. Organometallics
2001, 20, 2294. (c) Liu, S. H.; Lo, S. T.; Wen, T. B.; Zhou, Z. Y.; Lau,
C. P.; Jia, G. Organometallics 2001, 20, 667. (d) Bohanna, C.; Buil, M.
L.; Esteruelas, M. A.; On˜ate, E.; Valero, C. Organometallics 1999, 18,
5176. (e) Gotzig, J.; Otto, H.; Werner, H. J. Organomet. Chem. 1985,
287, 247. (f) Werner, H.; Meyer, U.; Peters, K.; von Schnering, H. G.
Chem. Ber. 1989, 122, 2097.
(31) (a) Esteruelas, M. A.; Lahoz, F. J.; On˜ate, E.; Oro, L. A.; Valero,
C.; Zeier, B. J. Am. Chem. Soc. 1995, 117, 7935. (b) Buil, M. L.;
Esteruelas, M. A. Organometallics 1999, 18, 1798.

Trimetallic Ru and Bimetallic Os Complexes
Organometallics, Vol. 24, No. 4, 2005 567
plexes 4 and 5 have âHRS values of 14.0 × 10-30 and
18.3 × 10-30 esu, respectively. Using the three-level
model,34 the static â0 values were calculated to be 8.7
× 10-30 and 13.8 × 10-30 esu, respectively. The â0 values
are close to those of 1,3,5-[(PPh3)AuCtC]3C6H3 (â0 ) 4
×
10-30 esu),14a 1,3,5-(CN)3-2,4,6-[Me2NCHdCH]3-
C6H3 (â0 ) 35 × 10-30 esu),17b and 1,3,5-(NO2)3-2,4,6-
[Me2NCHdCH]3C6H3 (â0 ) 24 × 10-30 esu).17a It is noted
that organometallic complexes 1,3,5-[Cl(dppe)2RuCt
CC6H4CtC]3C6H3 (â0 ) 94 × 10-30 esu)6a and 1,3,5-[Cl-
(dppm)2RuCtCC6H4CHdCH]3C6H3 (â0 ) 165 × 10-30
esu),6c which have a more extended structure, have
significantly larger â0 values.
Summary. By reacting RuHCl(CO)(PPh3)3 with 1,3,5-
triethynylbenzene, the trimetallic complex 1,3,5-[Cl-
(CO)(PPh3)2RuCHdCH]3C6H3 was obtained. 1,3,5-[Cl-
(CO)(PPh3)2RuCHdCH]3C6H3 was found to react with
PMe3 and pyridine ligands L (L ) pyridine (Py) and
4-phenylpyridine (PhPy)) to give 1,3,5-[Cl(CO)(PMe3)3-
RuCHdCH]3C6H3 and 1,3,5-[Cl(CO)(L)(PPh3)2RuCHd
CH]3C6H3 (L ) Py, PhPy). It was reported previously
that OsHCl(CO)(PPh3)3 does not undergo an insertion
reaction with PhCtCH. However, we found that OsHCl-
(CO)(PPh3)3 does undergo insertion reactions with ArCt
CH (Ar ) Ph, p-tolyl) to produce the six-coordinated
insertion products OsCl(CHdCHAr)(CO)(PPh3)3. Reac-
tion of OsHCl(CO)(PPh3)3 with 1,3,5-triethynylbenzene
was found to produce the bimetallic complex 1-HCtC-
3,5-[Cl(CO)(PPh3)3OsCHdCH]2C6H3 rather than a tri-
metallic complex. The electrochemical studies show the
metal centers in 1,3,5-[Cl(CO)(L)(PPh3)2RuCHdCH]3C6H3
(L ) Py, PhPy) interact with each other electronically.
The complexes [Cl(CO)(PMe3)3RuCHdCH]3C6H3 and
[Cl(CO)(Py)(PPh3)2RuCHdCH]3C6H3 exhibit second-
order NLO properties as suggested by HRS measure-
ments.
Figure 3. Cyclic voltammogram of 1,3,5-[Cl(CO)(Py)-
(PPh3)2RuCHdCH]3C6H3 (5) in 0.10 M n-Bu4NClO4/CH2-
Cl2 (Pt electrode, V vs Ag/AgCl, scan rate 100 mV/s, 25 °C).
The three oxidation waves were not resolved in the
cyclic votammogram of complexes 3 and 4, however. The
cyclic votammogram of complex 3 showed an irreversible
oxidation peak at 0.98 V vs Ag/AgCl. The cyclic votam-
mogram of complex 4 showed two irreversible oxidation
peaks at 0.76 and 1.05 V vs Ag/AgCl, which can be
tentatively attributed to the formation of 4+ (Ru(II)/Ru-
(II)/Ru(III)) and 43+ (Ru(III)/Ru(III)/Ru(III)), respec-
tively. Apparently, the peak separation between the
second and the third oxidation wave is too small to be
observed. We have conducted the CV experiments at
lower temperature (0 °C) to improve the reversibility.
However, the cyclovotamograms did not change ap-
preciably.
The electrochemical behaviors of complexes 3-6 can
be related to those of recently reported {Cp*Co(2,3-
Et2C2B4H3-7-CtC)}3C6H3 (11), {Cp*Co(2,3-Et2C2B4H3-
5-CtC)}3C6H3 (12), and {Cp*Co(2,3-Et2C2B3H4-5-Ct
C)}3C6H3 (13).2f Complex 11 has three oxidation waves
where the separation between the first and second
waves (0.2 V) is larger than that between the second
and third waves (0.1 V). Complex 12 shows only two
oxidation waves, and the second and third oxidation
waves are not resolved. Complexes 13 has only one
reduction wave.
The electrochemical properties of the related acetylide
compounds such as 1,3,5-[Cp(PPh3)2RuCtC]3C6H3,4
1,3,5-[Cp*(dppe)FeCtC]3C6H3,3 and 1,3,5-[Cl(dppe)2MCt
CC6H4CtC]3C6H3 (M ) Ru,7 Os2b) have also been
reported. Three separated one-electron-oxidation waves
were also observed in complexes such as 1,3,5-[Cp-
(PPh3)2RuCtC]3C6H3 (0.22, 0.35, and 0.50 V vs SCE)4
and 1,3,5-[Cp*(dppe)FeCtC]3C6H3 (-0.225, -0.125, and
0.000 V vs SCE).3 The peak separations of 1,3,5-[Cp-
(PPh3)2RuCtC]3C6H3 are at 0.12 and 0.15 V. The peak
separations of 1,3,5-[Cp*(dppe)FeCtC]3C6H3 are at 0.13
and 0.13 V. However, only one single oxidation wave
Experimental Section
All manipulations were carried out at room temperature
under a nitrogen atmosphere using standard Schlenk tech-
niques, unless otherwise stated. Solvents were distilled under
nitrogen from sodium-benzophenone (hexane, diethyl ether,
THF, benzene) or calcium hydride (dichloromethane, CHCl3).
The starting materials 1,3,5-(HCtC)3C6H3,12 RuHCl(CO)-
(PPh3)3,35 and OsHCl(CO)(PPh3)3 were prepared according
35
to literature methods.
Microanalyses were performed by M-H-W Laboratories
(Phoenix, AZ). 1H, 13C{1H}, and 31P{1H} NMR spectra were
collected on a JEOL EX-400 spectrometer (400 MHz) or a
1
Bruker ARX-300 spectrometer (300 MHz). H and 13C NMR
chemical shifts are relative to TMS, and 31P NMR chemical
shifts are relative to 85% H3PO4.
(32) Zyss, J.; Ledoux, I. Chem. Rev. 1994, 94, 77.
(33) Examples of recent work: (a) Alcarz, G.; Euzenat, L.; Mongin,
O.; Katan, C.; Ledoux, I.; Zyss, J.; Blanchard-Desce, M.; Vaultier, M.
Chem. Commun. 2003, 2766. (b) Zyss, J.; Ledoux-Pak, I.; Weiss, H.
C.; Blaser, D.; Boese, R.; Thallapally, P. K.; Thalladi, V. R.; Desiraju,
G. R. Chem Mater. 2003, 15, 3063. (c) Brunel, J.; Mongin, O.; Jutand,
A.; Ledoux, I.; Zyss, J.; Blanchard-Desce, M. Chem. Mater. 2003, 15,
4139. (d) Le Bouder, T.; Maury, O.; Bondon, A.; Costuas, K.; Amouyal,
E.; Ledoux, I.; Zyss, J.; Le Bozec, H. J. Am. Chem. Soc. 2003, 125,
12284. (f) Cui, Y. Z.; Fang, Q.; Lei, H.; Xue, G.; Yu, W. T. Chem. Phy.
Lett. 2003, 377, 507. (g) Zhou, X.; Ren, A. M.; Feng, J. K.; Liu, X. J.
Chem. Phys. Lett. 2003, 373, 167.
was observed for the ferrocenyl complex 1,3,5-[CpFe-
(η5-C5H4)]3C6H3
and 1,3,5-[Cl(dppe)2MCtCC6H4Ct
16d
C]3C6H3 (M ) Ru,7 Os2b).
Hyperpolarizability. The nonlinear optical proper-
ties of octupolar molecules are receiving increasing
attention in recent years.32,33 The second-order optical
nonlinearities of complexes 4 and 5 have been deter-
mined by hyper-Raleigh scattering at 1064 nm. Com-
(34) Three-level model: Joffre, M.; Yaron, D.; Silbey, R. J.; Zyss, J.
J. Chem. Phys. 1992, 97, 5607.
(35) Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley, M. F.;
Wonchoba, E. R.; Parshall, G. W. Inorg. Synth. 1974, 15, 45.

568 Organometallics, Vol. 24, No. 4, 2005
Xia et al.
The electrochemical measurements were performed with a
PAR model 273 potentiostat. A three-component electrochemi-
cal cell was used with a glassy-carbon electrode as the working
electrode, a platinum wire as the counter electrode, and a Ag/
AgCl electrode as the reference electrode. The cyclic voltam-
mograms were collected with a scan rate of 100 mV/s in CH2Cl2
containing 0.10 M n-Bu4NClO4 as the supporting electrolyte.
The peak potentials reported were referenced to Ag/AgCl.
Under our experimental conditions, the oxidation wave of Fc/
Fc+ occurred at 0.51 V.
(20 mL) was stirred for 10 min. to give a yellow solution. The
volume of the reaction mixture was reduced to ca. 5 mL under
vacuum. Addition of ether (150 mL) to the residue produced a
yellow solid, which was collected by filtration, washed with
ether and hexane, and dried under vacuum. Yield: 0.54 g, 90%.
Anal. Calcd for C156H126Cl3N3O3P6Ru3: C, 69.75; H, 4.73.
Found: C, 69.82; H, 4.85. 31P{1H} NMR (acetone-d6, 121.5
1
MHz): δ 25.2 (s). H NMR (acetone-d6, 300.13 MHz): δ 6.00
(d, J(HH) ) 16.8 Hz, 3 H, RuCHdCH), 6.39 (s, 3 H, CH of
C6H3), 8.69 (d, J(HH) ) 16.8 Hz, 3 H, RuCH), 8.79 (br, 6 H,
o-H of Py), 7.03-7.78 (m, 111 H, other aromatic protons). 13C-
{1H} NMR (CD2Cl2, 75.5 MHz): δ 121.5 (s, CH of C6H3), 126.7
(s, m-C of Py), 137.5 (s, C of C6H3), 140.2 (RuCHdCH), 140.5
(s, p-C of Py), 147.7 (s, q-C of Py-Ph), 149.6 (t, J(PC) ) 14.0
Hz, RuCH), 203.6 (t, J(PC) ) 14.1 Hz, CO), 121.7-134.4 (m,
other aromatic signals).
1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3 (3). To a suspen-
sion of RuHCl(CO)(PPh3)3 (3.00 g, 3.15 mmol) in CH2Cl2 (80
mL) was slowly (in 20 min) added 1,3,5-triethynylbenzene
(0.190 g, 1.27 mmol in 10 mL of CH2Cl2). The reaction mixture
was stirred for an additional 15 min to give a red solution.
The volume of the reaction mixture was then reduced to ca.
10 mL under vacuum. Addition of ether (250 mL) to the residue
produced an orange-red solid, which was collected by filtration,
washed with ether and hexane, and dried under vacuum.
Yield: 2.15 g, 92%. Anal. Calcd for C123H99Cl3O3P6Ru3: C,
66.53; H, 4.79. Found: C, 66.70; H, 4.61. 31P{1H} NMR (C6D6,
OsCl(CHdCHPh)(CO)(PPh3)3 (8a). To a solution of OsH-
Cl(CO)(PPh3)3 (0.50 g, 0.48 mmol) in CH2Cl2 (50 mL) was
added HCtCPh (0.16 mL, 1.44 mmol). The reaction mixture
was stirred at RT for 30 min to give a clear orange solution,
which was then concentrated to ca. 1 mL. Addition of diethyl
ether (30 mL) to the residue produced a light pink solid. The
solid was collected by filtration, washed with diethyl ether (2
× 20 mL), and dried under vacuum. Yield: 0.39 g, 71%. Anal.
Calcd for C63H52ClOP3Os: C, 66.16; H, 4.58. Found: C, 66.03;
H, 4.70. 31P{1H} NMR (121.5 MHz, CDCl3, 298 K): δ -11.6
(br), -22.7 (br) (with an integration ratio of ca. 2:1). 1H NMR
(300.13 MHz, CDCl3, 298 K): δ 6.28 (d br, J(HH) ) 17.5 Hz,
1 H, ) CHPh), 6.66-7.49 (m, 50 H, PPh3, Ph), 7.78 (d br,
J(HH) ) 17.5 Hz, 1 H, OsCH). 31P{1H} NMR (161.7 MHz,
toluene-d8, 203 K): δ -11.6 (d, J(PP) ) 12.1 Hz), -24.6 (t,
1
121.5 MHz): δ 29.9 (s). H NMR (C6D6, 300.13 MHz): δ 6.20
(d, J(HH) ) 13.2 Hz, 3 H, RuCHdCH), 6.72 (s, 3 H, CH of
C6H3), 7.25 (m, 54 H, PPh3), 8.03 (m, 36 H, PPh3), 8.84 (d,
J(HH) ) 13.2 Hz, 3 H, RuCH). 13C{1H} NMR (C6D6, 75.5
MHz): δ 118.5 (s, CH of C6H3), 127.3-134.5 (m, PPh3), 137.2
(s, RuCHdCH), 139.1 (s, C of C6H3), 146.7 (t, J(PC) ) 8.3 Hz,
RuCH), 202.4 (t, J(PC) ) 13.7 Hz, CO).
1,3,5-[Cl(CO)(PMe3)3RuCHdCH]3C6H3 (4). To a Schlenk
flask containing 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3 (1.20
g, 0.540 mmol) was added a THF solution of PMe3 (10 mL, 1
M, 10 mmol). The reaction mixture was stirred for 5 days to
give a light yellow solution with some white suspension. The
solvent was removed under vacuum, and acetone (100 mL) was
added to the residue. The resulting mixture was stirred for 3
h to give a light yellow solution with a white precipitate, which
was removed by filtration. The volume of the yellow filtrate
was reduced to ca. 5 mL under vacuum. Addition of ether (100
mL) to the residue produced a light yellow solid, which was
collected by filtration, washed with ether and hexane, and
dried under vacuum. Yield: 0.49 g, 68%. Anal. Calcd for C42H90-
Cl3O3P6Ru3: C, 37.89; H, 6.81. Found: C, 37.91; H, 6.64. 31P-
{1H} NMR (CD2Cl2, 121.5 MHz): δ -20.0 (t, J(PP) ) 22.6 Hz),
-7.8 (d, J(PP) ) 22.6 Hz). 1H NMR (acetone-d6, 300.13 MHz):
δ 1.48 (t, J(PH) ) 3.5 Hz, 54 H, PMe3), 1.57 (d, J(PH) ) 6.8
Hz, 27 H, PMe3), 6.65 (ddt, J(HH) ) 17.8 Hz, J(PH) ) 6.3, 2.6
Hz, 3 H, RuCHdCH), 7.02 (s, 3 H, CH of C6H3), 8.13 (ddt,
J(HH) ) 17.8 Hz, J(PH) ) 7.9, 3.4 Hz, 3 H, RuCH). 13C{1H}
NMR (CD2Cl2, 100.40 MHz): δ 16.9 (t, J(PC) ) 15.5 Hz, PMe3),
20.3 (d, J(PC) ) 20.6 Hz, PMe3), 117.3 (s, CH of C6H3), 135.9
(t, J(PC) ) 5.1 Hz, RuCHdCH), 141.7 (d, J(PC) ) 6.4 Hz, C of
C6H3), 163.0 (dt, J(PC) ) 76.9, 16.6 Hz, RuCH), 202.4 (q, J(PC)
) 12.2 Hz, CO).
1
J(PP) ) 12.1 Hz). H NMR (400 MHz, toluene-d8, 203 K): δ
6.60-7.60 (m, 51 H, dCHPh, PPh3), 8.32 (d br, J(HH) ) 14.0
Hz, 1 H, OsCH). 13C{1H} NMR (100.40 MHz, CDCl3, 298 K):
δ 123.9-142.3 (m, PPh3, Ph), 135.5 (br, dCHPh, confirmed
by a 1H-13C COSY NMR experiment), 147.7 (br, OsCH,
confirmed by a 1H-13C COSY NMR experiment), 182.3 (t,
J(PC) ) 8.4 Hz, CO).
OsCl(CHdCH(p-tolyl))(CO)(PPh3)3 (8b). To a solution of
OsHCl(CO)(PPh3)3 (0.45 g, 0.43 mmol) in CH2Cl2 (50 mL) was
added HCtC(p-tolyl) (0.16 mL, 1.30 mmol). The reaction
mixture was stirred at RT for 30 min to give a clear orange
solution, which was then concentrated to ca. 1 mL. Addition
of diethyl ether (30 mL) to the residue produced a light pink
solid. The solid was collected by filtration, washed with diethyl
ether (2 × 20 mL), and dried under vacuum. Yield: 0.33 g,
66.3%. Anal. Calcd for C64H54ClOP3Os: C, 66.40; H, 4.70.
Found: C, 66.30; H, 4.90. 31P{1H} NMR (121.5 MHz, CD2Cl2,
298 K): δ -11.1 (br), -22.7 (br) (with an integration in a ratio
of ca. 2:1). 1H NMR (300.13 MHz, CD2Cl2, 298 K): δ 2.24 (s, 3
H, CH3), 6.10 (d br, J(HH) ) 17.2 Hz, 1 H, ) CH(p-tolyl)),
6.48-7.36 (m, 49 H, PPh3, p-tolyl), 7.63 (d br, J(HH) ) 17.5
Hz, 1 H, OsCH). 31P{1H} NMR (121.5 MHz, CD2Cl2, 200 K):
1
δ -10.9 (d, J(PP) ) 11.4 Hz), -23.1 (t, J(PP) ) 11.4 Hz). H
1,3,5-[Cl(CO)(Py)(PPh3)2RuCHdCH]3C6H3 (5). A mix-
ture of [Cl(CO)(PPh3)2RuCHdCH]3C6H3 (0.200 g, 0.09 mmol)
and pyridine (0.2 mL) in CH2Cl2 (10 mL) was stirred for 10
min to give a yellow solution. The volume of the reaction
mixture was reduced to ca. 5 mL under vacuum. Addition of
ether (40 mL) to the residue produced a yellow solid, which
was collected by filtration, washed with ether and hexane, and
dried under vacuum. Yield: 0.16 g, 73%. Anal. Calcd for
NMR (300.13 MHz, CD2Cl2, 200 K): δ 2.21 (s, 3 H, CH3), 6.12
(d br, J(HH) ) 13.2 Hz, 1 H, CH(p-toyl)), 6.56-7.70 (m, 50 H,
PPh3, p-toyl, OsCH). 13C{1H} NMR (75.5 MHz, CD2Cl2, 298
K): δ 21.0 (s, CH3), 124.8-139.6 (m, other PPh3, C6H4), 135.8
1
(br, dCH(p-toyl), confirmed by a H-13C COSY NMR experi-
1
ment), 144.4 (br, OsCH, confirmed by a H-13C COSY NMR
experiment), 182.2 (t, J(PC) ) 8.1 Hz, CO).
C
138H114Cl3N3O3P6Ru3: C, 67.39; H, 4.68. Found: C, 67.58; H,
1-HCtC-3,5-[Cl(CO)(PPh3)3OsCHdCH]2C6H3 (9). To a
CH2Cl2 solution (20 mL) of OsHCl(CO)(PPh3)3 (200 mg, 0.192
mmol) was slowly (in 1 h) added 1,3,5-triethynylbenzene (15.8
mg, 0.106 mmol in 10 mL of CH2Cl2). The reaction mixture
was stirred for 15 min to give a light brown solution. The
volume of the reaction mixture was reduced to ca. 5 mL under
vacuum. Addition of ether (25 mL) to the residue produced a
white solid, which was collected by filtration, washed with
ether and hexane, and dried under vacuum. Yield: 0.169 g,
79%. Anal. Calcd for C122H98Cl2O2P6Os2: C, 65.61; H, 4.42.
4.57. 31P{1H} NMR (C6D6, 121.5 MHz): δ 26.1 (s). 1H NMR
(C6D6, 300.13 MHz): δ 6.11 (dd, J(HH) ) 6.6, 6.3 Hz, 6 H,
m-H of Py), 6.43 (d, J(HH) ) 16.6 Hz, 3 H, RuCHdCH), 6.61
(t, J(HH) ) 7 0.6 Hz, 3 H, p-H of Py), 6.87 (s, 3 H, CH of C6H3),
7.0-7.8 (m, 90 H, PPh3), 8.91 (br, 6 H, o-H of Py), 9.02 (dt,
J(HH) ) 16.3 Hz, J(PH) ) 2.9 Hz, 3 H, RuCH).
1,3,5-[Cl(CO)(PhPy)(PPh3)2RuCHdCH]3C6H3 (6). A mix-
ture of 1,3,5-[Cl(CO)(PPh3)2RuCHdCH]3C6H3 (0.500 g, 0.225
mmol) and 4-phenylpyridine (0.300 g, 1.93 mmol) in CH2Cl2

Trimetallic Ru and Bimetallic Os Complexes
Organometallics, Vol. 24, No. 4, 2005 569
Found: C, 65.79; H, 4.85. 31P{1H} NMR (CD2Cl2, 121.5 MHz):
δ -11.9 (br), -23.4 (br). 1H NMR (C6D6, 300.13 MHz, 298 K):
δ 3.15 (br, 1 H, CtCH), 6.07 (br, 2 H, OsCHdCH), 6.37 (br, 2
H, CH of C6H3), 6.79 (br, 1 H, CH of C6H3), 7.85 (br, 2 H,
OsCH).
C511-C516, C621-C626, C631-C636) after initial full-matrix
least-squares refinement due to the rotational disorder, which
were then refined with similar C-C distances and planarity
restraints. All of the hydrogen atoms in 5 and 8b were placed
in the ideal positions and refined as riding atoms. Further
details on crystal data, data collection, and refinements are
summarized in Table 1.
1-HCtC-3,5-[Cl(CO)(PPh3)2(PMe3)OsCHdCH]2C6H3 (10).
To a Schlenk flask containing 1-HCtC-3,5-[Cl(CO)(PPh3)3-
OsCHdCH]2C6H3 (0.50 g, 0.22 mmol) was added a THF
solution of PMe3 (10 mL, 1 M, 10 mmol). The reaction mixture
was stirred for 2 days to give a light yellow solution. The
volume of the mixture was reduced to ca. 3 mL under vacuum.
Addition of ether (30 mL) to the residue produced a white solid,
which was collected by filtration, washed with ether and
hexane, and dried under vacuum. Yield: 0.367 g, 88%. Anal.
Calcd for C92H86Cl2O2P6Os2: C, 59.38; H, 4.66. Found: C,
59.57; H, 4.73. 31P{1H} NMR (C6D6, 121.5 MHz): δ -55.8 (t,
J(PP) ) 12.9 Hz, PMe3), -12.4 (d, J(PP) ) 12.9 Hz, PPh3). 1H
NMR (C6D6, 300.13 MHz): δ 1.26 (d, J(PH) ) 7.4 Hz, PMe3),
2.85 (s, 1 H, tCH), 6.25 (dm, J(HH) ) 13.5 Hz, 2 H, OsCHd
CH), 6.46 (s, 1 H, CH of C6H3), 6.89 (s, 2 H, CH of C6H3), 7.0-
8.1 (m, PPh3), 8.75 (ddt, J(HH) ) 13.5 Hz, J(PH) ) 7.5, 2.2
Hz, 2 H, OsCH). 13C{1H} NMR (CD2Cl2, 75.5 MHz): δ 117.0
(s, C of C6H3), 122.6 (s, C of C6H3), 120.2 (s, CH of C6H3), 123.6
(s, CH of C6H3), 127.1-135.7 (m, PPh3), 142.2 (d, J(PC) ) 6.0
Hz, OsCHdCH), 148.5 (dt, J(PC) ) 62.4, 14.2 Hz, OsCH), 203.6
(q, J(PC) ) 9.2 Hz, CO).
HRS Experiments. IR laser pulses generated with an
injection-seeded Q-switched and mode-locked Nd:YAG laser
(Antares 76-S, 1064 nm, 70 ps, 15 Hz) were focused on a
cylindrical cell (6 mL) containing the sample. The fundamental
intensity was altered by rotation of a half-wave plate placed
between crossed polarizers and measured with a photodiode.
An efficient condenser system was used to collect the light
scattered at the harmonic frequency (532 nm) that was
detected by a photomultiplier. Discrimination of the second-
harmonic light from the fundamental light was accomplished
by a monochromator. Actual values of the intensities were
retrieved by using fast gated integrators and boxcar averagers.
All measurements were performed in chloroform using p-
nitroaniline (â ) 7.0 × 10-30 esu) as a reference. The intrinsic
â value was obtained after removing the contribution from the
multiphoton absorption-induced fluorescence that can interfere
with the HRS signal.38 Further details of the experimental
setup, data collection, and treatment can be found elsewhere.39
Crystallographic Details. Crystals suitable for X-ray
diffraction were grown from CH2Cl2 solutions of 5 and 8b
layered with hexane. Data collections were performed on a
Bruker SMART CCD area detector for 5, and on a Bruker Apex
CCD area detector for 8b, by using graphite-monochromated
Mo KR radiation (λ ) 0.71073 Å). Empirical absorption
corrections (SADABS)36 were applied. Both structures were
solved by direct methods, expanded by difference Fourier
syntheses, and refined by full-matrix least-squares on F2 using
the Bruker SHELXTL (Version 5.10)37 program package. All
non-hydrogen atoms were refined anisotropically except those
for the solvating CH2Cl2 molecule in 5, which was disordered
over two sites and refined with isotropic thermal parameters
using fixed C-Cl distances restraints. Some of the PPh3
ligands in 5 exhibited distorted phenyl rings (C131-C136,
Acknowledgment. The authors acknowledge finan-
cial support from the Hong Kong Research Grants
Council (HKUST6187/00P).
Supporting Information Available: Tables of bond
distances and angles, atomic coordinates and equivalent
isotropic displace coefficients, and anisotropic displacement
coefficients for 1,3,5-[Cl(CO)(Py)(PPh3)2RuCHdCH]3C6H3 (5)
and OsCl(CHdCH(p-tolyl))(CO)(PPh3)3 (8b). The materials are
available free of charge via the Internet at http://pubs.acs.org.
OM0496939
(38) Hsu, C. C.; Huang, T. H.; Zang, Y. L.; Lin, J. L.; Cheng, Y. Y.;
Lin, J. T.; Wu, H. H.; Wang, C. H.; Kuo, C. T.; Chen, C. H. J. Appl.
Phys. 1996, 80 (10), 5996.
(39) (a) Clays, K.; Persoons, A. Rev. Sci. Instrum. 1992, 63, 3285.
(b) Houbrechts, S.; Clays, K.; Persoons, A.; Pikramenou, Z.; Lehn, J.-
M. Chem. Phys. Lett. 1996, 258, 485.
(36) Sheldrick, G. M. SADABS, Empiracal Absorption Correction
Program; University of Go¨ttingen, Germany, 1996.
(37) Bruker. SHELXTL Reference Manual (Version 5.1); Bruker
Analytical X-Ray Systems Inc.: Madison, WI, 1997.