Reactions of SiH-functionalized cyclopentadienes with metal carbonyls

Article abstract of DOI:10.1021/om070204p

Thermal treatment of the SiH-functionalized cyclopentadienes (RC ₅H₄)SiHMeR′ [R = H, R′ = Ph (1), PhCH ₂ (2); R = t-Bu, R′ = Ph (3), PhCH₂ (4)] with Ru₂(CO)₁₂ gave the cyclic dinuclear metal complexes trans-[(R′MeSi)(η⁵-RC₅H₃)Ru(CO) ₂]₂ [R = H, R′ = Ph (7), PhCH₂ (8); R = f-Bu, R′ = Ph (10), PhCH₂ (H)] containing two Si-Ru bonds via Si-H activation. A cyclopentenyl complex, [(η²-C ₅H₇)SiMe(CH₂Ph)Ru(CO)₃]₂ (9), bridged by a vinylsilyl ligand was also obtained from the reaction, but reactions of the SiH-functionalized tetramethylcyclopentadienes (C ₅Me₄H)SiHMeR′ [R′ = Ph (5), PhCH₂ (6)] with Ru₃(CO)₁₂ only gave the cyclic diruthenium complex [(PhMeSi)(η-C₅Me₄)]Ru₂(CO) ₆ (12) with one Si-Ru bond and the desilylation product [(η⁵-C₅Me₄H)Ru(CO)]₂(μ-CO) ₂ (13). When 2 and 4 reacted with M(CO)₆, the similar cyclic dinuclear complexes trans-[(PhCH₂MeSi)(η-RC ₅H₃)M(CO)₃]₂ [R = H, M = W (18); R = t-Bu, M = Mo (15), W (20)] were obtained, in addition to the desilylation products [(η-RC₅H₄)M-(CO)₃]₂ [R = H, M = Mo (14), W (19); R = t-Bu, M = Mo (16), W (21)], but reactions of 6 with M(CO)₆ only gave the desilylation products [(η-C ₅Me₄H)M(CO)₃]₂ [M = Mo (17); M = W (22)]. The molecular structures of 7, 9, 12, 13, 15, 18, and 20 were determined by X-ray diffraction.

Full text of DOI:10.1021/om070204p

4212
Organometallics 2007, 26, 4212-4219
Reactions of SiH-Functionalized Cyclopentadienes with Metal
Carbonyls
Dafa Chen,† Jian Guo,† Shansheng Xu,† Haibin Song,† and Baiquan Wang*,†,‡
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai UniVersity, Tianjin
300071, and State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China
ReceiVed March 6, 2007
Thermal treatment of the SiH-functionalized cyclopentadienes (RC5H4)SiHMeR′ [R ) H, R′ ) Ph (1),
PhCH2 (2); R ) t-Bu, R′ ) Ph (3), PhCH2 (4)] with Ru3(CO)12 gave the cyclic dinuclear metal complexes
trans-[(R′MeSi)(η5-RC5H3)Ru(CO)2]2 [R ) H, R′ ) Ph (7), PhCH2 (8); R ) t-Bu, R′ ) Ph (10), PhCH2
(11)] containing two Si-Ru bonds via Si-H activation. A cyclopentenyl complex, [(η2-C5H7)SiMe(CH2-
Ph)Ru(CO)3]2 (9), bridged by a vinylsilyl ligand was also obtained from the reaction, but reactions of the
SiH-functionalized tetramethylcyclopentadienes (C5Me4H)SiHMeR′ [R′ ) Ph (5), PhCH2 (6)] with Ru3-
(CO)12 only gave the cyclic diruthenium complex [(PhMeSi)(η5-C5Me4)]Ru2(CO)6 (12) with one Si-Ru
bond and the desilylation product [(η5-C5Me4H)Ru(CO)]2(µ-CO)2 (13). When 2 and 4 reacted with M(CO)6,
the similar cyclic dinuclear complexes trans-[(PhCH2MeSi)(η5-RC5H3)M(CO)3]2 [R ) H, M ) W (18);
R ) t-Bu, M ) Mo (15), W (20)] were obtained, in addition to the desilylation products [(η5-RC5H4)M-
(CO)3]2 [R ) H, M ) Mo (14), W (19); R ) t-Bu, M ) Mo (16), W (21)], but reactions of 6 with
M(CO)6 only gave the desilylation products [(η5-C5Me4H)M(CO)3]2 [M ) Mo (17); M ) W (22)]. The
molecular structures of 7, 9, 12, 13, 15, 18, and 20 were determined by X-ray diffraction.
Our initial idea is to link the functional group, one of the
multiple components of the addition reaction, to a cyclopenta-
dienyl ring as a functionalized side chain and then to study the
reactions of the side-chain-functionalized cyclopentadienes with
metal carbonyls. Because the cyclopentadienyl ligand is a strong
Introduction
Since the first complex containing an M-Si bond was
synthesized by Wilkinson and co-workers in 1956,1 silyl
transition-metal chemistry has grown enormously and a large
number of new complexes have been prepared due to their broad
applications in industry.2 One of the most effective methods
for the preparation of these complexes is by the reactions of
transition-metal complexes with hydrosilanes via Si-H activa-
tion.2,3 Furthermore, activation of Si-H bonds is also very
important in industrial processes such as hydrosilylation, de-
hydrogenative silylation, and polysilane production.2,4 It is
widely considered that oxidative addition of the Si-H bond to
a metal center is one of the crucial steps in these processes.2-5
Metal carbonyl, especially Ru3(CO)12, has been extensively
used to catalyze multiple-component addition reactions, gener-
ally involving activation of C-H and other bonds.6 These
reactions are very useful in organic synthesis and in industry;
however, the mechanisms for most reactions are still unclear.
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Shimada, S.; Rao, M. L. N.; Li, Y. H.; Tanaka, M. Organometallics 2005,
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Chemistry; Wiley: New York, 2000; Chapter 12.8, p 401. (b) Kim, B. H.;
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V.; Sirlin, C.; Pfeffer, M. Chem. ReV. 2002, 102, 1731. (c) Dyson, P. J.
Coord. Chem. ReV. 2004, 248, 2443. (d) Morimoto, T.; Kakiuchi, K. Angew.
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* To whom correspondence should be addressed. Fax: 86-22-23504781.
E-mail: bqwang@nankai.edu.cn.
† Nankai University.
‡ Chinese Academy of Sciences.
(1) Piper, T. S.; Lemal, D.; Wilkinson, G. Naturwissenschaften 1956,
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10.1021/om070204p CCC: $37.00 © 2007 American Chemical Society
Publication on Web 07/18/2007

Reactions of SiH-Functionalized Cyclopentadienes
Organometallics, Vol. 26, No. 17, 2007 4213
Compound 3. Using a procedure similar to that described above,
compound 3 (9.87 g, 41 mmol) was synthesized from PhMeSiHCl
(12.5 g, 80 mmol) and (t-BuC5H4)Li (80 mmol) in 51% yield as a
yellow oil (bp 89-92 °C/0.5 mmHg). 1H NMR (CDCl3): δ 7.42-
7.34 (m, 2H, ArH), 7.26-7.08 (m, 3H, ArH), 6.84 (m), 6.66 (m),
6.55-5.86 (m), 3.38 (m), 2.88 (m) (total 4H, CpH), 4.98, 4.62,
4.09 (q, q, q, total 1H, SiH), 1.02, 0.98 (s, s, total 9H, CMe3), 0.34
(m), 0.27 (d, J ) 3.00 Hz), 0.01 (d, J ) 3.56 Hz) (total 3H, SiMe).
EI-MS: m/z 242 (11, M+).
Compound 4. Using a procedure similar to that described above,
compound 4 (11.3 g, 44 mmol) was synthesized from (PhCH2)-
MeSiHCl (13.6 g, 80 mmol) and (t-BuC5H4)Li (80 mmol) in 55%
yield as a yellow oil (bp 90-100 °C/0.3 mmHg). 1H NMR
(CDCl3): δ 7.40-7.30 (m, 2H, ArH), 7.27-7.12 (m, 3H, ArH),
7.05-6.06 (m), 3.48 (m), 3.13-2.97 (m), 2.48-2.30 (m) (total 4H,
CpH), 4.73, 4.41, 3.91 (m, m, m, total 1H, SiH), 2.30-2.19 (m,
2H, SiCH2), 1.35-1.27 (m, 9H, CMe3), 0.32 (m), 0.18 (d, J )
2.84 Hz), -0.03 (d, J ) 3.61 Hz) (total 3H, SiMe). EI-MS: m/z
256 (15, M+).
ligand to complex with a metal, it can be used as a trapping
tool to catch the possible intermediate for the metal carbonyl
catalyzed multiple-component addition reaction. The structures
and reactions of the possible intermediate may help us to deeply
understand the reaction mechanism. In recent studies we have
shown the reactions of pyridyl side-chain-functionalized cyclo-
pentadienes with metal carbonyl, which gave some novel
intramolecular C-H-activated products.7 Because hydrosilanes
are also one of the important components for the metal carbonyl
catalyzed multiple-component addition reaction,6a,c,8 and as part
of a systematic study of the reactions of functionalized cyclo-
pentadienes with metal carbonyls,7 in this work we studied the
reactions of the SiH-functionalized cyclopentadienes with metal
carbonyls, and a series of cyclic dinuclear metal complexes with
two Si-M bonds were obtained via Si-H activation.
Experimental Section
General Considerations. Schlenk and vacuum line techniques
were employed for all manipulations of air- and moisture-sensitive
compounds. All solvents were distilled from appropriate drying
Compound 5. Using a procedure similar to that described above,
compound 5 (5.03 g, 21 mmol) was synthesized from PhMeSiHCl
(12.5 g, 80 mmol) and (C5Me4H)Li (80 mmol) in 26% yield as a
yellow oil (bp 88-96 °C/0.25 mmHg). 1H NMR (CDCl3): δ 7.50-
7.15 (m, 5H, ArH), 5.05, 4.44 (m, m, total 1H, SiH), 3.04, 2.61 (s,
s, total 1H, CpH), 1.88-1.58 (m, total 12H, CpMe), 0.33 (m), 0.00
(m) (total 3H, SiMe). EI-MS: m/z 242 (100, M+).
1
agents under argon before use. H NMR spectra and mass spectra
were recorded on a Bruker AV300 and TRACE DSQ, respectively,
while IR spectra were recorded as KBr disks on a Nicolet 5DX
FT-IR spectrometer. Elemental analyses were performed on a
Perkin-Elmer 240C analyzer.
Compound 6. Using a procedure similar to that described above,
compound 6 (15.2 g, 59 mmol) was synthesized from (PhCH2)-
MeSiHCl (13.6 g, 80 mmol) and (C5Me4H)Li (80 mmol) in 74%
yield as a yellow oil (bp 94-98 °C/0.08 mmHg). 1H NMR
(CDCl3): δ 7.39-7.29 (m, 2H, ArH), 7.26-7.08 (m, 3H, ArH),
4.74, 4.19 (m, m, total 1H, SiH), 3.07, 2.26 (s, s, total 1H, CpH),
2.18-1.88 (m, total 14H, SiCH2 and CpMe), 0.20 (d, J ) 2.77
Hz), 0.01 (d, J ) 3.50 Hz) (total 3H, SiMe). EI-MS: m/z 256 (52,
M+).
Preparation of SiH-Functionalized Cyclopentadienes. The
SiH-functionalized cyclopentadienes 1-6 were prepared using
methods similar to those described in the literature.9 A 12.5 g (80
mmol) sample of PhMeSiHCl was quickly added to the suspension
of CpLi in THF at 0 °C, which was prepared from C5H6 (5.8 g, 88
mmol) in 100 mL of THF and n-BuLi (40 mL, 80 mmol) in
n-hexane. The mixture was stirred overnight. After filtration the
volatiles were removed under reduced pressure. The resulting oil
was distilled, and the yellow fraction at 57-60 °C/0.07 mmHg was
1
Reaction of 1 with Ru3(CO)12. A solution of 0.300 g (0.469
mmol) of Ru3(CO)12 and 0.262 g (1.41 mmol) of 1 in 30 mL of
heptane was refluxed for 12 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3 column.
Elution with CH2Cl2/petroleum ether developed a colorless band,
which gave 0.050 g (0.070 mmol, 10%) of 7 as colorless crystals.
Mp: >300 °C. Anal. Calcd for C28H24O4Ru2Si2: C, 49.25; H, 3.54.
collected (10.0 g, yield 67%), which was characterized as 1. H
NMR (CDCl3): δ 7.42-7.32 (m, 2H, ArH), 7.25-7.12 (m, 3H,
ArH), 6.80-6.20 (m), 3.61-3.42 (m), 2.89 (m) (total 5H, CpH),
4.61, 3.94 (q, q, total 1H, SiH), 0.31 (d, J ) 3.73 Hz), 0.00 (d, J
) 3.73 Hz) (total 3H, SiMe). EI-MS: m/z 186 (63, M+).
Compound 2. Using a procedure similar to that described above,
compound 2 (15.0 g, 75 mmol) was synthesized from (PhCH2)-
MeSiHCl (13.6 g, 80 mmol) and CpLi (80 mmol) in 94% yield as
1
Found: C, 49.50; H, 3.71. H NMR (CDCl3): δ 7.50-7.40 (m,
1
4H, ArH), 7.33-7.23 (m, 6H, ArH), 5.62 (m, 2H, CpH), 5.60-
5.55 (m, 4H, CpH), 5.39 (m, 2H, CpH), 0.83 (s, 6H, SiMe). IR
(νCO, cm-1): 1999(s), 1946(s).
a yellow oil (bp 64-66 °C/0.07 mmHg). H NMR (CDCl3): δ
7.40-7.27 (m, 2H, ArH), 7.24-7.10 (m, 3H, ArH), 7.00-6.55 (m),
3.04 (m), 2.48-2.30 (m), 2.21 (d, J ) 3.60 Hz) (total 5H, CpH),
4.42, 3.83 (q, q, total 1H, SiH), 2.26 (t, 2H, SiCH2), 0.31 (d, J )
3.63 Hz), 0.00 (d, J ) 3.20 Hz) (total 3H, SiMe). EI-MS: m/z 200
(35, M+).
Reaction of 2 with Ru3(CO)12. Using a procedure similar to
that described above, reaction of 2 (0.282 g, 1.41 mmol) with Ru3-
(CO)12 (0.300 g, 0.469 mmol) gave 8 (0.050 g, 0.063 mmol, 9%)
and 9 (0.060 g, 0.077 mmol, 11%) as colorless and yellow crystals,
respectively. The following are data for 8. Mp: 190-192 °C dec.
Anal. Calcd for C30H28O4Ru2Si2: C, 50.69; H, 3.97. Found: C,
(7) Chen, D.; Li, Y.; Wang, B.; Xu, S.; Song, H. Organometallics 2006,
25, 307.
(8) (a) Seki, Y.; Takeshita, K.; Kawamoto, K.; Murai, S.; Sonoda, N. J.
Org. Chem. 1986, 51, 3890. (b) Seki, Y.; Takeshita, K.; Kawamoto, K. J.
Organomet. Chem. 1989, 369, 117. (c) Chatani, N.; Fukumoto, Y.; Ida, T.;
Murai, S. J. Am. Chem. Soc. 1993, 115, 11614. (d) Hilal, H. S.; Khalaf, S.;
Jondi, W. J. Organomet. Chem. 1993, 452, 167. (e) Kakiuchi, F.; Tanaka,
Y.; Chatani, N.; Murai, S. J. Organomet. Chem. 1993, 456, 45. (f) Misumi,
Y.; Ishii, Y.; Hidai, M. Organometallics 1995, 14, 1770. (g) Monteil, F.;
Matsuda, I.; Alper, H. J. Am. Chem. Soc. 1995, 117, 4419. (h) Furukawa,
N.; Kourogi, N.; Seki, Y.; Kakiuchi, F.; Murai, S. Organometallics 1999,
18, 3767. (i) Kakiuchi, F.; Igi, K.; Matsumoto, M.; Chatani, N.; Murai, S.
Chem. Lett. 2001, 30, 422. (j) Fukumoto, Y.; Sawada, K.; Hagihara, M.;
Chatani, N.; Murai, S. Angew. Chem., Int. Ed. 2002, 41, 2779. (k) Kakiuchi,
F.; Igi, K.; Matsumoto, M.; Hayamizu, T.; Chatani, N.; Murai, S. Chem.
Lett. 2002, 31, 396. (l) Kakiuchi, F.; Tsuchiya, K.; Matsumoto, M.;
Mizushima, E.; Chatani, N. J. Am. Chem. Soc. 2004, 126, 12792. (m)
Kakiuchi, F.; Matsumoto, M.; Tsuchiya, K.; Igi, K.; Hayamizu, T.; Chatani,
N.; Murai, S. J. Organomet. Chem. 2004, 686, 134.
1
51.10; H, 4.23. H NMR (CDCl3): δ 7.10 (t, 4H, ArH), 7.01 (t,
2H, ArH), 6.73 (d, J ) 7.53 Hz, 4H, ArH), 5.38 (m, 2H, CpH),
5.27 (m, 4H, CpH), 5.06 (t, 2H, CpH), 2.43 (d, J ) 7.13 Hz, 4H,
SiCH2), 0.38 (s, 6H, SiMe). IR (νCO, cm-1): 2006(s), 1950(s). The
following are data for 9. Mp: 98-99 °C. Anal. Calcd for C32H34O6-
1
Ru2Si2: C, 49.73; H, 4.43. Found: C, 49.51; H, 4.52. H NMR
(CDCl3): δ 7.27-6.85 (m, 10H, ArH), 6.14 (m), 5.66 (m), 5.54
(s). 5.41 (s), 5.19 (s), 5.10 (s), 5.02 (s), 4.86 (s), 4.76 (s) (total 2H,
vinyl H), 2.81-1.24 (m, 16H, (CH2)3 and PhCH2), 0.60 (s), 0.50
(s), 0.42 (s), 0.38 (s), 0.31 (s), 0.26 (s), 0.24 (s), 0.21 (s), 0.19 (s),
0.07 (s) (total 6H, SiMe). IR (νCO, cm-1): 2018(s), 1987(s), 1965-
(s), 1952(m).
Reaction of 3 with Ru3(CO)12. A solution of 0.300 g (0.469
mmol) of Ru3(CO)12 and 0.341 g (1.41 mmol) of 3 in 30 mL of
heptane was refluxed for 12 h. Monitored by TLC, a little 3 still
(9) Ciruelo, G.; Cuenca, T.; Gomez, R.; Gomez-Sal, P.; Martin, A. J.
Chem. Soc., Dalton Trans. 2001, 1657.

4214 Organometallics, Vol. 26, No. 17, 2007
Table 1. Crystal Data and Summary of X-ray Data Collection for 7, 9, 12, 13, and 15
Chen et al.
7
9
12
13
15
empirical formula
fw
C28H24O4Ru2Si2
684.81
C32H34O6Ru2Si2
772.91
C22H20O6Ru2Si
610.61
C22H26O4Ru2
556.57
C40H44Mo2O6Si2
868.81
T, K
294(2)
294(2)
294(2)
293(2)
294(2)
radiation (λ), Å
cryst syst
space group
a, Å
b, Å
c, Å
Mo KR (0.71073)
monoclinic
P2(1)/n
12.478(2)
8.4064(13)
13.557(2)
90
109.067(2)
90
1344.0(4)
2
Mo KR (0.71073)
Mo KR (0.71073)
monoclinic
P2(1)/n
9.438(4)
11.766(4)
21.820(8)
90
92.076(6)
90
2421.5(16)
4
Mo KR (0.71073)
monoclinic
P2(1)/n
7.472(2)
14.960(4)
9.964(3)
90
107.405(4)
90
1062.7(5)
2
Mo KR (0.71073)
triclinic
triclinic
P1h
P1h
8.574(2)
12.807(3)
16.875(4)
70.257(4)
79.676(4)
71.357(4)
1647.2(7)
2
9.7330(15)
9.9833(16)
10.5532(17)
80.329(2)
86.341(3)
74.622(2)
974.5(3)
1
R, deg
â, deg
γ, deg
V, Å 3
Z
D
calcd, g‚cm-3
1.692
1.245
684
1.558
1.030
780
1.675
1.330
1208
1.739
1.445
556
1.481
0.749
444
µ, mm-1
F(000)
cryst size, mm
θ range, deg
0.20 × 0.14 × 0.12
1.93-26.39
7325
2735/0.0394
164
0.24 × 0.20 × 0.12
1.29-25.01
8338
5760/0.0336
389
0.24 × 0.20 × 0.16
1.87-26.69
13268
4952/0.0298
285
0.20 × 0.18 × 0.14
2.54-26.42
6058
2179/0.0223
131
0.40 × 0.22 × 0.20
1.96-26.34
5509
3909/0.0160
230
no. of reflns collected
no. of independent reflns/Rint
no. of params
GOF on F2
0.998
1.029
1.057
1.072
1.071
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
0.0308, 0.0669
0.0552, 0.0768
0.0434, 0.0823
0.0955, 0.1022
0.0265, 0.0568
0.0412, 0.0622
0.0205, 0.0486
0.0281, 0.0514
0.0283, 0.0676
0.0359, 0.0724
remained in the solvent. The solvent was removed under reduced
pressure. The residue was washed with hexane to give 0.080 g of
a white solid (10a). The filtrate was removed under reduced pressure
and then placed in an Al2O3 column. Elution with CH2Cl2/petroleum
ether developed a colorless band, which gave 0.050 g (0.063 mmol,
9%) of 10 as colorless crystals. The following are data for 10. Mp:
225-226 °C. Anal. Calcd for C36H40O4Ru2Si2: C, 54.39; H, 5.07.
Reaction of 2 with Mo(CO)6. A solution of 0.500 g (1.89 mmol)
of Mo(CO)6 and 0.379 g (1.89 mmol) of 2 in 30 mL of xylene was
refluxed for 4 h. The solvent was removed under reduced pressure,
and the residue was placed in an Al2O3 column. Elution with CH2-
Cl2/petroleum ether developed a red band, which gave 0.040 g
(0.081 mmol, 9%) of the known complex 14.10 Mp: 215 °C dec.
1H NMR (CDCl3): δ 5.30 (s, 10H, CpH). IR (νCO, cm-1): 1952-
(s), 1917(m), 1887(s).
1
Found: C, 54.10; H, 5.10. H NMR (CDCl3): δ 7.50-7.40 (m,
4H, ArH), 7.32-7.23 (m, 6H, ArH), 5.44 (m, 4H, CpH), 5.36 (t,
2H, CpH), 1.20 (s, 18H, CMe3), 0.81 (s, 6H, SiMe). IR (νCO, cm-1):
2000(s), 1943(s). The following are data for 10a. 1H NMR
(CDCl3): δ 7.56-7.48 (m, 2H, C6H5), 7.38-7.28 (m, 3H, C6H5),
5.50 (br s, 1H, CpH), 5.34 (m, 1H, CpH), 5.32 (m, 1H, CpH), 1.280
(s, 9H, CMe3), 0.81 (s, 3H, SiMe). IR (νCO, cm-1): 1999(s), 1948-
(s), 1940(s), 1913(m).
Reaction of 4 with Ru3(CO)12. Using a procedure similar to
that described above, reaction of 4 (0.361 g, 1.41 mmol) with
Ru3(CO)12 (0.300 g, 0.469 mmol) gave 11 (0.052 g, 0.063 mmol)
as colorless crystals in 9% yield. Mp: 245-247 °C dec. Anal.
Calcd for C38H44O4Ru2Si2: C, 55.45; H, 5.39. Found: C, 55.80;
H, 5.10. 1H NMR (CDCl3): δ 7.08 (t, 4H, ArH), 6.98 (t, 2H, ArH),
6.69 (d, J ) 7.02 Hz, 4H, ArH), 5.23 (t, 2H, CpH), 5.10 (t, 2H,
CpH), 4.88 (t, 2H, CpH), 2.41 (d, J ) 1.42 Hz, 4H, SiCH2), 1.17
(s, 18H, CMe3), 0.33 (s, 6H, SiMe). IR (νCO, cm-1): 1997(s),
1940(s).
Reaction of 4 with Mo(CO)6. Using a procedure similar to that
described above, reaction of 4 (0.484 g, 1.89 mmol) with Mo(CO)6
(0.500 g, 1.89 mmol) gave 15 (0.050 g, 0.057 mmol, 6%) and 16
(0.065 g, 0.107 mmol, 12%) as colorless and red crystals,
respectively. The following are data for 15. Mp: 242 °C dec. Anal.
Calcd for C40H44Mo2O6Si2: C, 55.30; H, 5.10. Found: C, 55.78;
H, 4.99. 1H NMR (CDCl3): δ 7.13 (t, 4H, ArH), 7.03 (t, 2H, ArH),
6.75 (d, J ) 6.90 Hz, 4H, ArH), 5.55 (t, 2H, CpH), 5.38 (t, 2H,
CpH), 4.53 (t, 2H, CpH), 2.48 (q, 4H, CH2), 1.18 (s, 18H, CMe3),
0.53 (s, 6H, SiMe). IR (νCO, cm-1): 1992(s), 1922(s), 1889(s). The
following are data for 16. Mp: 155 °C dec. Anal. Calcd for C24H26-
1
Mo2O6: C, 47.86; H, 4.35. Found: C, 48.10; H, 4.80. H NMR
(CDCl3): δ 5.27 (br s, 4H, CpH), 5.10 (br s, 4H, CpH), 1.25 (s,
18H, CMe3). IR (νCO, cm-1): 1940(s), 1893(s).
Reaction of 2 with W(CO)6. A solution of 0.500 g (1.42 mmol)
of W(CO)6 and 0.285 g (1.42 mmol) of 2 in 30 mL of xylene was
refluxed for 5 days. The solvent was removed under reduced
pressure, and the residue was placed in an Al2O3 column. Elution
with CH2Cl2/petroleum ether developed two bands. The first band
(red) gave 0.035 g (0.053 mmol, 9%) of the known complex 19.11
The second band (colorless) gave 0.045 g of 18 (0.048 mmol, 7%)
as colorless crystals. The following are data for 18. Mp: 270 °C
dec. Anal. Calcd for C32H28W2O6Si2: C,41.22; H, 3.03. Found: C,
Reaction of 5 with Ru3(CO)12. Using a procedure similar to
that described above, reaction of 5 (0.341 g, 1.41 mmol) with Ru3-
(CO)12 (0.300 g, 0.469 mmol) gave 12 (0.082 g, 0.134 mmol, 19%)
and 13 (0.012 g, 0.021 mmol, 3%) as yellow and orange crystals,
respectively. The following are data for 12. Mp: 130-132 °C dec.
Anal. Calcd for C22H20O6Ru2Si: C, 43.27; H, 3.30. Found: C,
42.90; H, 3.05. 1H NMR (CDCl3): δ 7.70 (m, 2H, ArH), 7.37 (m,
3H, ArH), 2.24 (s, 3H, CpMe), 2.13 (s, 3H, CpMe), 1.95 (s, 3H,
CpMe), 1.23 (s, 3H, CpMe), 0.81 (s, 3H, SiMe). IR (νCO, cm-1):
2082(m), 2042(m), 2006(s), 1991(s), 1969(m), 1924(m). The
following are data for 13. Mp: 210-211 °C dec. Anal. Calcd for
1
41.40; H, 3.15. H NMR (CDCl3): δ 7.11 (t, 4H, ArH), 7.02 (t,
2H, ArH), 6.73 (d, J ) 7.09 Hz, 4H, ArH), 5.77 (d, J ) 1.68 Hz,
2H, CpH), 5.53 (br s, 4H, CpH), 4.54 (d, J ) 1.68 Hz, 2H, CpH),
2.52 (q, 4H, CH2), 0.54 (s, 6H, SiMe). IR (νCO, cm-1): 2000(s),
1925(s), 1883(s). The following are data for 19.11 Mp: 238-240 °C.
1
C22H26O4Ru2: C, 47.48; H, 4.71. Found: C, 46.93; H, 5.11. H
NMR (CDCl3): δ 4.66 (s, 2H, CpH), 1.90 (s, 12H, CpMe), 1.85
(s, 12H, CpMe). IR (νCO, cm-1): 1929(s), 1755(s).
Reaction of 6 with Ru3(CO)12. Using a procedure similar to
that described above, reaction of 6 (0.361 g, 1.41 mmol) with Ru3-
(CO)12 (0.300 g, 0.469 mmol) only gave 13 (0.024 g, 0.042 mmol)
in 6% yield.
(10) Ginley, D. S.; Bock, C. R.; Wrighton, M. S. Inorg. Chim. Acta 1977,
23, 85.
(11) (a) Abrahamson, H. B.; Heeg, M. J. Inorg. Chem. 1984, 23, 2281.
(b) Verdonck, L.; Bossuyt, A. R.; Verpoort, P. F.; Geeraert, J.; Van de
Vondel, D.; Van der Kelen, G. P. J. Mol. Catal. 1992, 76, 319. (c) Aime,
S.; Cordero, L.; Gobetto, R.; Szalontai, G. Spectrochim. Acta 1993, 49A,
1307.

Reactions of SiH-Functionalized Cyclopentadienes
Organometallics, Vol. 26, No. 17, 2007 4215
Table 2. Crystal Data and Summary of X-ray Data
Collection for 18 and 20
Table 3. Selected Bond Distances (Å) and Angles (deg)
Compound 7
18
20
Ru(1)-Si(1)
C(3)-Si(1A)
Si(1)-C(8)
2.4001(11) Ru(1)-C(3)
2.261(4)
1.895(4)
1.907(4)
1.882(4)
Si(1)-C(9)
empirical formula
fw
C32H28W2O6Si2
932.42
294(2)
C40H44W2O6Si2
1044.63
294(2)
C(3)-Ru(1)-Si(1) 100.48(9)
Si(1A)-C(3)-Ru(1) 128.76(17)
C(3A)-Si(1)-Ru(1) 122.43(11)
T, K
radiation (λ), Å
cryst syst
space group
a, Å
Mo KR (0.71073)
monoclinic
P2(1)/c
11.111(3)
13.783(3)
11.075(3)
90
107.598(4)
90
1616.6(6)
2
Mo KR (0.71073)
triclinic
P1h
Compound 9
2.8875(8) Ru(1)-Si(1)
2.4195(17) Ru(1)-C(28)
Ru(1)-Ru(2)
Ru(2)-Si(2)
Ru(1)-C(29)
Ru(2)-C(16)
Si(1)-C(7)
Si(2)-C(28)
Si(2)-C(27)
C(28)-C(29)
2.4178(18)
2.475(5)
2.493(6)
1.894(6)
1.879(6)
1.899(6)
1.364(8)
9.7235(19)
10.012(2)
10.540(2)
80.436(3)
86.223(3)
74.183(3)
973.3(3)
1
b, Å
c, Å
2.477(6)
2.471(5)
1.911(6)
1.869(6)
1.870(6)
1.385(8)
Ru(2)-C(15)
Si(1)-C(15)
Si(1)-C(14)
Si(2)-C(20)
C(15)-C(16)
R, deg
â, deg
γ, deg
V, Å 3
Z
D
C(28)-Ru(1)-Ru(2) 81.22(14)
C(28)-Si(2)-Ru(2) 108.93(18)
C(28)-Ru(1)-C(29) 32.48(19)
C(15)-Ru(2)-Ru(1) 81.33(14)
C(15)-Si(1)-Ru(1) 108.75(19)
Si(2)-Ru(2)-Ru(1) 73.58(4)
Si(2)-C(28)-Ru(1) 93.9(2)
Si(1)-Ru(1)-Ru(2) 74.22(5)
Si(1)-C(15)-Ru(2) 93.5(2)
C(16)-Ru(2)-C(15) 31.89(19)
calcd, g‚cm-3
1.915
7.225
888
1.782
6.011
508
µ, mm-1
F(000)
cryst size, mm
θ range, deg
no. of reflns collected
0.22 × 0.20 × 0.18 0.28 × 0.24 × 0.20
2.43-26.36
1.96-25.01
4970
Compound 12
2.8628(9) Ru(1)-C(13)
2.4834(11) Si(1)-C(13)
8850
Ru(1)-Ru(2)
Ru(2)-Si(1)
2.253(3)
1.897(3)
C(13)-Ru(1)-Ru(2) 82.06(6)
Si(1)-C(13)-Ru(1) 102.75(11)
no. of independent reflns/Rint 3280/0.0295
3399/0.0243
230
1.041
no. of params
216
GOF on F2
1.012
Si(1)-Ru(2)-Ru(1) 74.50(2)
C(13)-Si(1)-Ru(2) 100.55(8)
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
0.0226, 0.0436
0.0388, 0.0481
0.0312, 0.0721
0.0382, 0.0756
Compound 15
Mo(1)-Si(1A)
C(4)-Si(1)
2.6294(8) Mo(1)-C(4)
2.342(2)
1.882(3)
1H NMR (CDCl3): δ 5.38 (s, 10H, CpH). IR (νCO, cm-1): 1948-
(s), 1910(m), 1875(s).
1.890(2)
1.907(3)
Si(1)-C(13)
Si(1)-C(14)
C(4)-Mo(1)-Si(1A) 93.24(6)
Si(1)-C(4)-Mo(1) 131.64(12)
C(4)-Si(1)-Mo(1A) 116.09(8)
Reaction of 4 with W(CO)6. Using a procedure similar to that
described above, reaction of 4 (0.364 g, 1.42 mmol) with W(CO)6
(0.500 g, 1.42 mmol) gave 20 (0.030 g, 0.029 mmol, 4%) and 21
(0.040 g, 0.051 mmol, 7%) as colorless and red crystals, respec-
tively. The following are data for 20. Mp: 275 °C dec. Anal. Calcd
for C40H44W2O6Si2: C,45.99; H, 4.25. Found: C, 46.47; H, 4.58.
1H NMR (CDCl3): δ 7.13 (t, 4H, ArH), 7.03 (t, 2H, ArH), 6.77
(d, J ) 6.90 Hz, 4H, ArH), 5.66 (t, 2H, CpH), 5.47 (t, 2H, CpH),
4.53 (t, 2H, CpH), 2.50 (q, 4H, CH2), 1.19 (s, 18H, CMe3), 0.55
(s, 6H, SiMe). IR (νCO, cm-1): 1992(s), 1919(s), 1887(s). The
following are data for 21. Mp: 194 °C dec. Anal. Calcd for
Compound 18
2.6252(12) W(1)-C(4)
W(1)-Si(1)
2.362(4)
1.877(5)
C(4)-Si(1A)
Si(1)-C(10)
1.895(4)
1.900(4)
93.67(10)
Si(1)-C(9)
C(4)-W(1)-Si(1)
C(4A)-Si(1)-W(1) 114.80(14)
Si(1A)-C(4)-W(1) 133.0(2)
Compound 20
W(1)-Si(1A)
Si(1)-C(4)
Si(1)-C(14)
C(4)-W(1)-Si(1A) 93.49(14)
Si(1)-C(4)-W(1)
2.6235(16) W(1)-C(4)
2.331(5)
1.883(6)
1.903(6)
1.908(6)
Si(1)-C(13)
C(4)-Si(1)-W(1A) 115.97(17)
1
C24H26W2O6: C, 37.04; H, 3.37. Found: C, 37.11; H, 3.57. H
131.1(3)
NMR (CDCl3): δ 5.71 (t, 4H, CpH), 5.40 (t, 4H, CpH), 1.31 (s,
18H, CMe3). IR (νCO, cm-1): 1935(s), 1885(s).
Chart 1
Reaction of 6 with Mo(CO)6. Using a procedure similar to that
described above, reaction of 6 (0.484 g, 1.89 mmol) with Mo(CO)6
(0.500 g, 1.89 mmol) only gave the desilylation complex 17 (0.040
g, 0.066 mmol, 7%) as red crystals. Mp: 159 °C dec. Anal. Calcd
for C24H26Mo2O6: C,47.86; H, 4.35. Found: C, 48.31; H, 4.85. 1H
NMR (CDCl3): δ 4.89 (s, 2H, CpH), 2.01 (s, 12H, CpMe), 1.94
(s, 12H, CpMe). IR (νCO, cm-1): 1920(s), 1889(s).
Results and Discussion
Reaction of 6 with W(CO)6. Using a procedure similar to that
described above, reaction of 6 (0.364 g, 1.42 mmol) with W(CO)6
(0.500 g, 1.42 mmol) only gave the desilylation complex 22 (0.050
g, 0.064 mmol, 9%) as red crystals. Mp: 205 °C dec. Anal. Calcd
for C24H26W2O6: C, 37.05; H, 3.37. Found: C, 37.43; H, 3.40. 1H
NMR (CDCl3): δ 5.26 (s, 2H, CpH), 2.06 (s, 12H, CpMe), 2.03
(s, 12H, CpMe). IR (νCO, cm-1): 1920(s), 1882(s).
Crystallographic Studies. Single crystals of complexes 7, 9,
12, 13, 15, 18, and 20 suitable for X-ray diffraction were obtained
from hexane/CH2Cl2 solution. Data collection was performed on a
Bruker SMART 1000, using graphite-monochromated Mo KR
radiation (ω-2θ scans, λ ) 0.71073 Å). Semiempirical absorption
corrections were applied for all complexes. The structures were
solved by direct methods and refined by full-matrix least squares.
All calculations were using the SHELXL-97 program system. The
crystal data and summary of X-ray data collection are presented in
Tables 1 and 2. Selected bond lengths and angles are listed in
Table 3.
The SiH-functionalized cyclopentadienes 1-6 were prepared
from the corresponding Cp′Li (Cp′ ) C5H5, t-BuC5H4, C5Me4H)
and RMeSiHCl (R ) Ph, PhCH2) in 26-94% yields. 1, 2, 5,
and 6 exist mainly as a mixture of two isomers (A and B in
Chart 1) with ratios of about 2.9:1, 2.5:1, 12.5:1, and 2.3:1,
respectively, while 3 and 4 exist mainly as a mixture of three
isomers (A, B, and C in Chart 1) with ratios of about 2.5:1:0.5
and 2:1:0.7, respectively, based on the characteristic peaks of
SiH (quadriplex or multiplet) and SiMe (doublet) protons in
their 1H NMR spectra (Supporting Information). All the EI mass
spectra of 1-6 show the molecular ion peaks; among them the
molecular ion peak of 5 appears as the basic peak. However,
no satisfied elemental analysis for 1-6 was obtained. This is
probably due to the fact that the SiH-containing compounds
1-6 cannot be combusted completely, which leads to the
formation of SiC and makes the found values of carbon much
lower than the calculated values.

4216 Organometallics, Vol. 26, No. 17, 2007
Chen et al.
Scheme 1
Scheme 2
Figure 1. ORTEP diagram of 7. Thermal ellipsoids are shown at
the 30% level.
Thermal treatment of CpSiHMePh (1) with Ru3(CO)12 in
refluxing heptane afforded the cyclic dinuclear complex trans-
[(PhMeSi)(η5-C5H4)Ru(CO)2]2 (7) in 10% yield (Scheme 1).
The Si-H bond was activated, and two Si-Ru bonds were
formed in the molecule. This kind of complex was reported to
be prepared by the thermal rearrangement reactions of the
corresponding disilyl-bridged biscyclopentadienyltetracar-
bonyldiruthenium complexes in very low yields (2-6%)
(Scheme 2).12 Therefore, this work provided a new synthetic
route for this kind of complex, especially with different
1
substituents at the silicon atom. The H NMR spectrum of 7
shows three groups of peaks for the Cp protons at 5.62, 5.57,
and 5.39 ppm and one singlet for the SiMe protons at 0.83 ppm,
indicating the existence of only one isomer. Single-crystal X-ray
diffraction analysis showed that it is a trans isomer (Figure 1).
The IR spectrum of 7 shows two terminal carbonyl absorptions
at 1999 and 1946 cm-1
.
Similarly, reactions of (t-BuC5H4)SiHMePh (3) and (t-
BuC5H4)SiHMe(CH2Ph) (4) with Ru3(CO)12 also gave the cyclic
dinuclear complexes trans-[(PhMeSi)(η5-t-BuC5H3)Ru(CO)2]2
(10) and trans-[(PhCH2)MeSi(η5-t-BuC5H3)Ru(CO)2]2 (11) both
in 9% yield, but the reaction of CpSiHMe(CH2Ph) (2) with Ru3-
(CO)12 afforded a yellow complex, [(η2-C5H7)SiMe(CH2Ph)-
Ru(CO)3]2 (9) (11%), in addition to the analogous cyclic
dinuclear complex trans-[(PhCH2)MeSi(η5-C5H4)Ru(CO)2]2 (8)
1
(9%) (Scheme 1). The H NMR spectrum of 9 (Supporting
Information) shows at least nine groups of peaks at 6.14-4.76
ppm for the vinyl protons and ten groups of peaks at 0.60-
0.07 ppm for the SiMe protons, indicating that 9 exists as a
mixture of several isomers. However, the isomers cannot be
separated by TLC due to the almost equal Rf values or by
recrystallization. Single-crystal X-ray analysis revealed the
structure of one isomer, in which the cyclopentadienyl rings
were partially hydrogenated (Figure 2). In the 1H NMR spectrum
of 9, signals for the vinyl protons appeared at 6.14-4.76 ppm.
Their shifts were significantly downfield from those of the
bridged vinylsilyl ligands in [Cp*Ru(µ-H)]2[µ-η2:η2-HSiMe2-
(CHdCH2) (23) (4.50-3.72 ppm)15a and Cp*2Ru2(SiPh2CHd
CH2)(µ-η2-HSiPh2)(µ-H)(H) (24) (1.89-1.44 ppm),15b suggest-
Figure 2. (a) ORTEP diagram of 9. Thermal ellipsoids are shown
at the 30% level. (b) Molecular structure of 9 seen from the direction
of the Ru-Ru bond.
ing the reduced back-donation from the ruthenium center and
the weakened coordination of the CdC bond to the ruthenium
center. This is further supported by the single-crystal X-ray
diffraction analysis. The IR spectrum of 9 shows four terminal
carbonyl absorptions at 2018, 1987, 1965, and 1952 cm-1. The
1H NMR and IR spectra of complexes 8, 10, and 11 are similar
to those of 7 indicated similar structures.
The yields of all the products are low. The main reasons are
the formation of the polymeric products and the decomposition
of Ru3(CO)12 (the unreacted ligand precursors were monitored
(12) (a) Zhang, Y.; Xu, S.; Zhou, X. Organometallics 1997, 16, 6017.
(b) Zhang, Y.; Wang, B.; Xu, S.; Zhou, X.; Sun, J. J. Organomet. Chem.
1999, 584, 356. (c) Zhang, Y.; Wang, B.; Xu, S.; Zhou, X. Organometallics
2001, 20, 3829. (d) Zhang, Y.; Wang, B.; Xu, S.; Zhou, X. Chin. J. Chem.
2002, 20, 1388. (e) Chen, D.; Mu, B.; Xu, S.; Wang, B. J. Organomet.
Chem. 2006, 691, 3823.

Reactions of SiH-Functionalized Cyclopentadienes
Organometallics, Vol. 26, No. 17, 2007 4217
Chart 2
Scheme 3
at the end of the reaction). For the reaction of 3 with Ru3(CO)12,
the polymeric product 10a (Chart 2) was obtained as a white
solid. It is insoluble in hexane and slightly soluble in CHCl3
and cannot be developed by Al2O3 column. For other reactions,
the polymeric products were more insoluble and filtered off by
Figure 3. ORTEP diagram of 12. Thermal ellipsoids are shown
at the 30% level.
1
an Al2O3 column. The H NMR spectrum of 10a shows two
groups of multiplets at 7.56-7.48 (2H) and 7.38-7.28 (3H)
ppm for the phenyl protons, a broad singlet at 5.50 (1H) and
two multiplets at 5.34 (1H) and 5.32 (1H) ppm for the Cp
protons, a singlet at 1.28 (9H) for the t-butyl protons, and a
singlet at 0.81 (3H) ppm for the SiMe protons (Supporting
Information). Its IR spectrum shows four terminal carbonyl
absorptions at 1999(s), 1948(s), 1940(s), and 1913(m) cm-1
.
1
Its H NMR and IR data are similar to those of 10 but with a
little difference. The mass spectrum (ESI) shows complicated
peaks up to 2000 (the limit of the instrument), indicating the
polymeric structure.
When (C5Me4H)SiHMePh (5) reacted with Ru3(CO)12, a
yellow complex, [(PhMeSi)(η5-C5Me4)]Ru2(CO)6 (12), was
obtained, in addition to the desilylation product [(η5-C5Me4H)-
1
Ru(CO)]2(µ-CO)2 (13) (Scheme 3). The H NMR spectrum of
12 showed two groups of multiplets for the phenyl protons, four
singlets for CpMe protons at 2.24, 2.13, 1.95, and 1.23 ppm,
and a singlet for the SiMe protons at 0.81 ppm. The IR spectrum
of 12 showed six terminal carbonyl absorptions at 2082, 2042,
2006, 1991, 1969, and 1924 cm-1. Single-crystal X-ray analysis
revealed that it is a (tetramethylcyclopentadienyl)diruthenium
complex with a Si-Ru bond (Figure 3). However, reaction of
(C5Me4H)SiHMe(CH2Ph) (6) with Ru3(CO)12 only gave the
desilylation product 13.
Figure 4. ORTEP diagram of 15. Thermal ellipsoids are shown
at the 30% level.
Scheme 4
Considering the similarity of iron with ruthenium, reactions
of 1-6 with Fe(CO)5 and Fe2(CO)9 were also studied. However,
no product was monitored by TLC. This may be attributed to
the lower activity of iron carbonyl compared to Ru3(CO)12.13
When 4 reacted with Mo(CO)6 in refluxing xylene, the
analogous cyclic complex trans-[(PhCH2MeSi)(η5-t-BuC5H3)-
Mo(CO)3]2 (15) (6%) was also given, besides the desilylation
product [(η5-t-BuC5H4)Mo(CO)3]2 (16) (12%) (Scheme 4), while
reaction of 2 or (C5Me4H)SiHMe(CH2Ph) with Mo(CO)6 only
gave the desilylation product [(η5-C5H5)Mo(CO)3]2 (14) (9%)
or [(η5-C5Me4H)Mo(CO)3]2 (17) (7%). Similarly, the cyclic
dinuclear complexes trans-[(PhCH2MeSi)(η5-C5H4)W(CO)3]2
(18) (7%) and trans-[(PhCH2MeSi)(t-BuC5H3)W(CO)3]2 (20)
(4%) were also obtained by reactions of 2 and 4 with W(CO)6,
in addition to the desilylation complexes [(η5-C5H5)W(CO)3]2
(19) (9%) and [(η5-t-BuC5H4)Mo(CO)3]2 (21) (7%) (Scheme
4), but reaction of (C5Me4H)SiHMe(CH2Ph) with W(CO)6 only
gave the desilylation product [(η5-C5Me4H)W(CO)3]2 (22) (9%).
The molecular structures of 7, 9, 12, 13, 15, 18, and 20 were
determined by X-ray diffraction analysis (Figures 1-5 and
Supporting Information). The molecule of 7 consists of two
[PhMeSi(η5-C5H4)Ru(CO)2] moieties linked to each other by
two Si-Ru bonds. Like many analogues,12 7 has Ci symmetry.
(13) Biran, C.; Blum, Y. D.; Glaser, R.; Tse, D. S.; Youngdahl, K. A.;
Laine, R. M. J. Mol. Catal. 1988, 48, 183.

4218 Organometallics, Vol. 26, No. 17, 2007
Chen et al.
isomers) substitution at the two silicon atoms]. This agrees with
the 1H NMR data of 9, though only one isomer was determined
by X-ray diffraction analysis.
The structure of complex 12 is similar to that of [(Me2Ge)-
(η5-C5Me4)]Ru2(CO)6, synthesized by the reaction of C5Me4-
HMe2GeGeMe2C5Me4H with Ru3(CO)12.12c The Ru(2)-Si(1)
bond length is 2.4834(11) Å, much longer than those of 7
[2.4001(11) Å] and 9 [2.4178(18) and 2.4195(17) Å]. The Ru-
Ru distance is 2.8628(9) Å, close to that of [(Me2Ge)(η5-C5-
Me4)]Ru2(CO)6] [2.861(1) Å]11c and slightly longer than those
found in Ru3(CO)12 [2.854(1) Å].15 The four-membered ring
Ru(1)-Ru(2)-Si(1)-C(13) is almost coplanar, and the plane
is nearly perpendicular to the cyclopentadienyl plane (dihedral
angle 86.9°).
The structure of 13 is a trans form and has Ci symmetry,
similar to the cyclopentadienyl and pentamethylcyclopentadienyl
analogues.16,17 The two cyclopentadienyl ring planes are parallel.
Two carbonyls are bridged, and two carbonyls are terminal. The
Ru-Ru bond distance [2.7458(7) Å] is slightly longer than that
in trans-[η5-CpRu(CO)(µ-CO)]2 [2.735(2) Å]16 and comparable
with the value in [(η5-C5Me5)Ru(CO)(µ-CO)]2 [2.752(1) Å].17
Similar to that of 7, the structures of 15, 18, and 20 also
have Ci symmetry and consist of two [(PhCH2)MeSi(RC5H3)M-
(CO)3] moieties linked to each other by two Si-M bonds. The
six-membered rings (two Si atoms, two metal atoms, and two
bridgehead carbons), constituting their molecular frameworks,
also adopt standard chair conformations. The Mo-Si distance
[2.6294(8) Å] in 15 is close to those of [{Mo(µ-η2-HSiEt2)-
(CO)4}2] [2.6152(6) and 2.7093(6) Å].18 The W-Si distances
[2.6252(12) Å for 18, 2.6235(16) Å for 20] are in the range of
the tungsten-silyl bond distances (2.533-2.633 Å) in the
structurally related silyltungsten complexes Cp*(CO)2(L)WSiR3
(L ) PR′3, pyridine).2d,3c,l,o,19 This is the first report for this
kind of cyclic dinuclear molybdenum and tungsten complex,
although there are many examples for the iron and ruthenium
analogues.12,20
Figure 5. ORTEP diagram of 18. Thermal ellipsoids are shown
at the 30% level.
The six-membered ring Ru(1)-Si(1)-C(3A)-Ru(1A)-Si-
(1A)-C(3), constituting its molecular framework, adopts pre-
cisely a standard chair conformation. The Ru-Si distance
[2.4001(11) Å] is slightly shorter than that of the analogues
[Me2Si(η5-C5H4)Ru(CO)2]2 [2.4074(9) Å]12a and [Me2Si(η5-C5-
Me4)Ru(CO)2]2 [2.424(1) Å]12b and much shorter than those in
acyclic analogues [2.452(3)-2.507(8) Å].14
The structure of 9 (Figure 2a) shows that a double bond of
the cyclopentadienyl ring was hydrogenated. The two Ru atoms
are bridged by two vinylsilyl ligands, and the Ru-Ru distance
is 2.8875(8) Å. The Ru(1)-Si(1) and Ru(2)-Si(2) distances
[2.4178(18) and 2.4195(17) Å] are comparable with those in
the bridged silyl complexes 23 and 24 [2.421(2)-2.384(2)
Å].15a,b The C(15)-C(16) and C(28)-C(29) distances [1.364-
(8) and 1.385(8) Å] are in the range of normal CdC double
bonds, but shorter than those in the bridged silyl complexes 23
and 24 [1.406(9)-1.39(1) Å]15a,b and in the coordinated ethylene
in [Cp*Ru(µ-η2-CHdCH2)]2(η2-CH2dCH2) [1.389(13) Å] and
Cp*2Ru2(µ-CMedCHCHdCMe)(η2-CH2dCH2) [1.389(13) Å].15c
The Ru-C bond lengths [Ru(2)-C(15), Ru(2)-C(16), Ru(1)-
C(28), and Ru(1)-C(29)], varying from 2.471(5) to 2.493(6)
Å, are much longer than the corresponding Ru-C distances of
the bridged silyl complexes 23 [2.218(6) and 2.228(6) Å]15a and
24 [2.243(7) and 2.270(7) Å].15b These results and the NMR
data for the coordinated vinyl group strongly suggest that the
π-coordination of the vinyl group in methylphenylcyclopente-
nylsilane to the Ru atom was considerably weakend. The
structure of 9 has C2 symmetry. The C2 axis passes through the
midpoint of Ru(1)-Ru(2) and perpendicular with it. The
structure of 9 has a cis geometry with the two η2-cyclopentene
rings, and the substitution at the two silicon atoms is also of
cis geometry. However, 9 should have three cis isomers [cis-
η2-cyclopentene rings, cis (two isomers) or trans (one isomer)
substitution at the two silicon atoms] and three trans isomers
[trans-η2-cyclopentene rings, cis (one isomer) or trans (two
Conclusions
Reactions of the SiH-functionalized cyclopentadienes with
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Reactions of SiH-Functionalized Cyclopentadienes
Organometallics, Vol. 26, No. 17, 2007 4219
cyclic dinuclear metal complexes with one or two Si-M bonds
were obtained via Si-H activation. A novel cyclopentenyl
complex, [(η2-C5H7)SiMe(CH2Ph)Ru(CO)3]2 (9), bridged by a
vinylsilyl ligand was also obtained and characterized.
Program for New Century Excellent Talents in University (Grant
NCET-04-0229) for financial support.
Supporting Information Available: X-ray structural informa-
tion for complexes 7, 9, 12, 13, 15, 18, and 20, ORTEP figures of
13 and 20, and 1H NMR spectra of 1-6, 9, and 10a. This material
is available free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. We are grateful to the National Natural
Science Foundation of China (Grants 20421202, 20672058, and
20472034), the Research Fund for the Doctoral Program of
Higher Education of China (Grant 20030055001), and the
OM070204P