Synthesis and characterization of bimetallic ruthenium complexes bridged with linear C4H4 and C6H4O2 ligands

Article abstract of DOI:10.1021/om9804935

Reaction of Me₃SiC≡CC≡CSiMe₃ with RuHCl(CO)(PPh₃)₃ in CH₂Cl₂ produced RuCl(η¹-C(C≡CSiMe₃)=CHSiMe ₃)(CO)(PPh₃)₂, which on treatment wit

Full text of DOI:10.1021/om9804935

4762
Organometallics 1998, 17, 4762-4768
Articles
Syn th esis a n d Ch a r a cter iza tion of Bim eta llic Ru th en iu m
Com p lexes Br id ged w ith Lin ea r C4H4 a n d C6H4O2
Liga n d s
Hai Ping Xia, Richard C. Y. Yeung, and Guochen J ia*
Department of Chemistry, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon, Hong Kong
Received J une 15, 1998
Reaction of Me3SiCtCCtCSiMe3 with RuHCl(CO)(PPh3)3 in CH2Cl2 produced RuCl(η1-
C(CtCSiMe3)dCHSiMe3)(CO)(PPh3)2, which on treatment with dppe gave RuCl(η1-C-
(CtCSiMe3)dCHSiMe3)(CO)(PPh3)(dppe). Reaction of RuHCl(CO)(PPh3)3 with HCtCCtCH
generated in situ from the reaction of Me3SiCtCCtCSiMe3 with n-Bu4NF/NH4F/H2O
produced [RuCl(CO)(NH3)(PPh3)2]2(µ-CHdCHCHdCH), whereas the same reaction without
the NH4F afforded [RuCl(CO)(PPh3)2]2(µ-CHdCHCHdCH). Complex [RuCl(CO)(NH3)-
(PPh3)2]2(µ-CHdCHCHdCH) reacted with excess PEt3 and t-BuNC to give [RuCl(CO)(PEt3)3]2-
(µ-CHdCHCHdCH) and {[Ru(t-BuNC)3(PPh3)2]2(µ-COCHdCHCHdCHCO)}Cl2, respectively.
The structure of [RuCl(CO)(PEt3)3]2(µ-CHdCHCHdCH) has been confirmed by X-ray
diffraction.
In tr od u ction
many conjugated organic materials (for example, poly-
acetylenes, push/pull stilbenes, and polyenes) have only
The synthesis and characterization of bimetallic and
polymeric organometallic compounds with π-conjugated
bridges are attracting considerable interest.1,2 During
the past decades, a large number of conjugated orga-
nometallic bimetallic complexes with hydrocarbon chains
serving as σ,σ-, σ,π-, or π,π-bound bridging ligands have
been reported. Most of the conjugated organometallic
bimetallic complexes with σ,σ-bridging hydrocarbon
chains are those with metal-C(sp) linkages, for ex-
ample, Cx-bridged,3,4 bis(acetylide),5 bis(carbyne),6 bis-
(vinylidene),7 and bis(allenylidene) complexes.8
9
2
sp carbons in their backbones. Only a few complexes
with linear CnHn (n ) 2,10,11 4,12,13 5,14 615) bridges have
(4) See for example: (a) Gil-Rubio, J .; Laubender, M.; Werner, H.
Organometallics 1998, 17, 1202. (b) Guillemot, M.; Toupet, L.; Lapinte,
C. Organometallics 1998, 17, 1928. (c) Coat, F.; Guillevic, M. A.; Toupet,
L.; Paul, F.; Lapinte, C. Organometallics 1997, 16, 5988. (d) Werner,
H.; Lass, R. W.; Wolf, J . Organometallics 1997, 16, 4077. (e) Wood-
worth, B. E.; White, P. S.; Templeton, J . L. J . Am. Chem. Soc. 1997,
119, 828. (f) Akita, M.; Chung, M. C.; Sakurai, A.; Sugimoto, S.; Terada,
M.; Tanaka, M.; Moro-oka, Y. Organometallics 1997, 16, 4882. (g) Yam,
V. W. W.; Lau, V. C. Y.; Cheung, K. K. Organometallics 1996, 15, 1740.
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H. Organometallics 1993, 12, 1359. (n) Crescenzi, R.; Sterzo, C. L.
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only sp2-hybridized carbons are interesting because
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10.1021/om9804935 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 09/30/1998

Bimetallic Ruthenium Complexes
Organometallics, Vol. 17, No. 22, 1998 4763
Sch em e 1
been reported. Other reported bimetallics with metal-
C(sp2) linkages include complexes with C2R2 bridges,16,17
a
µ-1,4-PhCdCH-CHdCPh bridge,18 CHdCHArCHdCH
bridges,19 aryl bridges,20 and 1,3-bimetalated cyclobute-
nylidene (C4R3) bridges.21 Very recently, the C5H5N-
bridged complex (t-Bu3SiO)3NbdCH-CHdCH-CHd
CH-NdNb(OSi-t-Bu)3 was reported.22
In principle, insertion reactions of diacetylenes with
metal hydride complexes could provide an entry to
bimetallic complexes with metal vinyl linkages. How-
ever, such reactions have only been sparsely explored
for such purposes.14,19 In this report, we present the
synthesis and characterization of conjugated bimetal-
lic complexes derived from the insertion reactions of
RuHCl(CO)(PPh3)3 with HCtCCtCH.
which could then be desilylated to give [RuCl(CO)-
(PPh3)2]2(µ-C4H4). Thus, the reaction of Me3SiCtCCt
CSiMe3 with RuHCl(CO)(PPh3)3 was investigated.
Resu lts a n d Discu ssion
Rea ction of Me3SiCtCCtCSiMe3 w ith Ru HCl-
(CO)(P P h 3)3, P r epar ation of Ru Cl(η1-C(CtCSiMe3)d
CHSiMe3)(CO)(P P h 3)2. Insertion reactions of RCt
CR′ with RuHCl(CO)(PPh3)3 at room temperature to
give the five-coordinated vinyl complexes RuCl(CRd
CHR′)(CO)(PPh3)2 have been reported by several
groups.23-25 In principle, the hydride complex RuHCl-
(CO)(PPh3)3 (1) may react with 0.5 equiv of com-
mercially available Me3SiCtCCtCSiMe3 to give bis-
insertion products [RuCl(CO)(PPh3)2]2(µ-C4H2(SiMe3)2),
Addition of excess of Me3SiCtCCtCSiMe3 to a sus-
pension of RuHCl(CO)(PPh3)3 in CH2Cl2 produced an
orange-brown solution from which the mono-insertion
complex 2 was easily isolated as an orange-yellow solid
(Scheme 1). The presence of the C(CtCSiMe3)d
CHSiMe3 group in complex 2 is indicated by the 1H and
13C NMR spectra. In particular, the 1H NMR spectrum
(in CDCl3) showed the vinyl signal at 5.23 ppm and the
SiMe3 signals at 0.15 and 0.22 ppm; the 13C NMR
spectrum (in CDCl3) showed the SiMe3 signals at -1.1
and 0.8 ppm and the C3CH signals at 98.8 (s, tCSiMe3),
114.5 (s, tC), 143.1 (s, dCH), and 152.6 ppm (t, J (PC)
) 8.4 Hz, Ru-Cd). Reported complexes related to
complex 2 are RuCl(η1-C(CtCR)dCHR)(CO)(PPh3)2 (R
) t-Bu, n-Bu, CMe2OH, Ph, Cy, p-MeC6H4).25a,26-28 In
these complexes, C(CtCR)dCHR has been proposed to
be an η1 ligand, and this bonding mode in RuCl(η1-C(Ct
C-t-Bu)dCH-t-Bu)(CO)(PPh3)2 has been confirmed by
X-ray diffraction.28 Complex 2 has a color and 31P NMR
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4764 Organometallics, Vol. 17, No. 22, 1998
Xia et al.
Sch em e 2
data similar to those of the reported five-coordinated
25a,26,27
complexes RuCl(η1-C(CtCR)dCHR)(CO)(PPh3)2
and thus most likely has C(CtCSiMe3)dCHSiMe3 in an
η1 manner. The possibility of η3 bonding for C(Ct
CSiMe3)dCHSiMe3 in 2 cannot be excluded completely
in view of the fact that a number of complexes with η3-
C(CtCR)dCHR or η3-C(CtCR)dCHR′ ligands have
been reported.29 In addition, reaction of Me3SiCt
CCHdCHSiMe3 with RuHCl(CO)(PPh3)3 is reported to
give RuCl(CO)(C(CHdCHSiMe3)dCHSiMe3)(PPh3)2, in
which one of the olefin double bonds interacts with the
Ru center very weakly, as indicated by X-ray diffraction
study.24
HCtCCtCH might lead to the linear C4H4-bridged
bimetallic complex [RuCl(CO)(PPh3)2]2(µ-CHdCH-CHd
CH). Since terminal acetylenes RCtCH can be gener-
ated from the reactions of RCtCSiMe3 with base/ROH
or F- agents,30 we attempted to generate HCtCCtCH
from commercially available Me3SiCtCCtCSiMe3. Ini-
tially one-pot reactions of RuHCl(CO)(PPh3)3 with Me3-
SiCtCCtCSiMe3 in CH2Cl2 in the presence of desily-
lating reagents such as K2CO3/MeOH, KOH/MeOH,
NH4F, and n-Bu4NF were attempted, with a hope that
HCtCCtCH would be generated in situ and then react
to give the insertion product. Reactions of RuHCl(CO)-
(PPh3)3 with Me3SiCtCCtCSiMe3 in CH2Cl2 in the
presence of NH4F led to the formation of RuHCl(CO)-
(NH3)(PPh3)2 (4) as the predominant product. The same
compound can be obtained from the reactions of RuHCl-
(CO)(PPh3)3 with NH4F or aqueous NH3. Reaction of
RuHCl(CO)(PPh3)3 with Me3SiCtCCtCSiMe3 in CH2-
Cl2 in the presence of other desilylating reagents led to
uncharacterized mixtures.
It was found that the six-coordinated C4H4-bridged
bimetallic complex 5 could be prepared by bubbling the
vapor (presumably a mixture of HCtCCtCH, NH3,
THF) from a mixture of Me3SiCtCCtCSiMe3, NH4F,
n-Bu4NF on silica gel, and H2O in THF, with gentle
heating, through a suspension of RuHCl(CO)(PPh3)3 in
CH2Cl2 (Scheme 2). In this reaction, the C4H4-bridged
complex 5 was produced along with some uncharacter-
ized species. The amount of complex 5 formed appears
to be dependent on the reaction time and the rate of
bubbling. Pure samples of 5 could be obtained by
washing the crude product with a small amount of CH2-
Cl2. Complex 5 is likely produced from the reaction of
the complex [RuCl(CO)(PPh3)2]2(µ-C4H4) (6) with NH3.
Several closely related mononuclear complexes Ru-
(CHdCHR)Cl(L)(CO)(PPh3)2 have been reported re-
cently from the reactions of HCtCR with RuHCl(L)-
(CO)(PPh3)2 (L is a 2e nitrogen donor ligand).31 In the
latter reactions, five-coordinate intermediate Ru(CHd
CHR)Cl(CO)(PPh3)2 has been proposed. Both NH4F and
Bu4NF appear to be important for the formation of
complex 5. If only NH4F was used, the hydride complex
4 along with some uncharacterized species were pro-
duced. A black material and a small amount of complex
[RuCl(CO)(PPh3)2]2(µ-C4H4) (6) were formed if only
n-Bu4NF was used. Apparently, n-Bu4NF helps to
generate HCtCCtCH.
To clarify the structure, we have converted complex
2 into the air-stable complex RuCl(η1-C(CtCSiMe3)d
CHSiMe3)(CO)(PPh3)(dppe) (3) by treatment with dppe
(Scheme 1). The geometry of complex 3 can be readily
assigned based on 31P NMR and 13C NMR spectroscopic
data. The PPh3 is trans to one of the PPh2 groups of
dppe, as indicated by the large J (PPh3-PPh2) coupling
constant (307.7 Hz). The vinyl group is trans to the
other PPh2 group of the dppe ligand, as indicated by
2
the large J (PPh2-C) coupling constant (60.9 Hz). The
geometry around ruthenium in complex 3 is similar to
those of recently reported mononuclear complexes RuCl-
(CHdCHR)(CO)(PPh3)(PP) (PP ) dppm, dppe, and
dppp).19a The 13C signals of the CtC triple bond in 3
is very similar to those found with 2, suggesting at most
a weak interaction with the ruthenium center in 2.
It is probably not surprising that complex 2 is pro-
duced instead of RuCl(Me3SiCdCHCtCSiMe3)(CO)-
(PPh3)2. Reactions of HCtCR and PhCtCCtCPh with
RuHCl(CO)(PPh3)3 have been reported previously to
give RuCl(CHdCHR)(CO)(PPh3)2 and RuCl(C(CtCPh)d
CHPh)(CO)(PPh3)2, respectively.23-25 It is likely that
the regiochemistry for the insertion reaction of RuHCl-
(CO)(PPh3)3 with RCtCR′ is determined by steric effects
in that the larger group in the products tends to be as
far away as possible from the ruthenium center.
Complex 2 does not undergo further insertion reaction
with RuHCl(CO)(PPh3)3, as demonstrated by the reac-
tion of RuHCl(CO)(PPh3)3 with less than 1 equiv of Me3-
SiCtCCtCSiMe3 or the reaction of isolated 2 with
RuHCl(CO)(PPh3)3. Similarly complex 3 also failed to
undergo an insertion reaction with RuHCl(CO)(PPh3)3.
Steric effects are the likely reason for the low reactivity
of the CtC functional group in 2 and 3 toward insertion
reactions with RuHCl(CO)(PPh3)3. It was thought that
removal of the bulky SiMe3 group from 2 and 3 may
increase the reactivity of the CtC functional group
toward insertion reactions. Unfortunately, 2 and 3 did
not react with the desilylating agents NH4F or n-Bu4-
NF at room temperature and decomposed to an unde-
fined mixture in refluxing THF in the presence of NH4F
or n-Bu4NF.
P r ep a r a tion of [Ru Cl(CO)(NH3)(P P h 3)2]2(µ-CHd
CHCHdCH) an d [Ru Cl(CO)(P P h 3)2]2(µ-CHdCHCHd
CH). Since reactions of HCtCR with RuHCl(CO)-
(PPh3)3 usually give RuCl(CHdCHR)(CO)(PPh3)2, it was
anticipated that reaction of RuHCl(CO)(PPh3)3 with
The yield for complex 6 could be improved if HCt
CCtCH was generated slowly by dropping a THF
(29) See for example: (a) Yang, S. M.; Chan, M. C. W.; Cheung, K.
K.; Che, C. M.; Peng, S. M. Organometallics 1997, 16, 2819, and
references therein. (b) Bianchini, C.; Innocenti, P.; Peruzzini, M.;
Romerosa, A.; Zanobini, F. Organometallics 1996, 15, 272, and refer-
ences therein.
(30) Colvin, E. W. Silicon Reagents in Organic Synthesis; Academic
Press: London, 1988; Chaper 7, p 45.
(31) Santos, A.; Lo´pez, J .; Gala´n, A.; Gonza´lez, J . J .; Tinoco, P.;
Echavarren, A. M. Organometallics 1997, 16, 3482.

Bimetallic Ruthenium Complexes
Organometallics, Vol. 17, No. 22, 1998 4765
Sch em e 3
solution of n-Bu4NF into a prewarmed THF solution of
Me3SiCtCCtCSiMe3. In this way, complex 6 was
obtained along with uncharacterized species as a red-
dish-brown suspension in CH2Cl2. A slow dropping rate
of n-Bu4NF results in a better yield of complex 6. As
the solubility of complex 6 in organic solvents is poor,
pure samples of 6 could be obtained by washing the
crude product with acetone, chloroform, or CH2Cl2.
1
Compound 5 was characterized by 31P and H NMR,
IR spectroscopy, and elemental analysis. The presence
of NH3 in 5 is indicated by the observation of the 1H
signal at 0.86 ppm assignable to NH3 (in CDCl3) and
an IR band at 3374 cm-1 assignable to ν(N-H). The
1H chemical shift for NH3 in 5 is within the range
reported for other NH3 complexes, for example, 0.09
ppm with [Ru(CtCPh)(NH3)(dppe)2]PF632 and 2.28 ppm
with [Ru(CtCPh)(NH3)(PMe3)4]PF6.33 The presence of
1
the C4H4 bridge is indicated by the H NMR spectrum
which showed AA′BB′XX′ (X ) PPh3) vinyl signals at
4.63 and 5.89 ppm (Ru-CH). The C4H4 unit is assigned
a trans geometry because the 3J (H-H) coupling con-
stants are very similar to those reported for (1E,3E)-
Me3SnCHdCH-CHdCHSnMe3.34 The geometry around
ruthenium in complex 5 is assigned by analogy to those
of mononuclear complexes RuHCl(CHdCHR)(L)(CO)-
(PPh3)2, where L is a two-electron nitrogen donor lig-
and.31 Unfortunately, 5 is not soluble enough in com-
mon organic solvents to get a good 13C NMR spectrum.
5 and 6 reacted with PEt3 to give [RuCl(CO)(PEt3)3]2-
(µ-CHdCHCHdCH) (7). The PEt3 ligands in complex
7 are meridional, as indicated by the AM2 pattern 31P
NMR spectrum. The presence of the C4H4 bridge is
1
indicated by the H NMR spectrum (in CD2Cl2), which
showed the vinyl proton signals at 6.22 ppm (Ru-CHd
CH) and 6.64 ppm (Ru-CH)CH), and the 13C NMR
spectrum (in CD2Cl2), which showed the vinyl signals
at 144.7 ppm for â-CH and 151.6 ppm for R-CH. The
vinyl group is trans to the unique PEt3 ligand, as
indicated by the large 2J (C-PEt3) coupling constant
(74.4 Hz). The structure has been confirmed by an
X-ray diffraction study (see below).
1
Compound 6 has also been characterized by 31P and H
NMR, IR spectroscopy, and elemental analysis. Again
poor solubility in common organic solvents precluded a
good 13C NMR spectrum.
Previously reported C4H4-bridged bimetallic com-
plexes are limited to [CpFe(LL′)]2(µ-CHdCHCHdCH)
(LL′ ) (CO)2, dppm, (CO)(PPh3), (CO)(PMe3)).12,13 The
complex [CpFe(CO)2]2(µ-CHdCHCHdCH) was prepared
from the reaction of [CpFe(CO)2]- with cis-dichlorocy-
clobutene,12 and [CpFe(LL′)]2(µ-CHdCHCHdCH) (LL′
) dppm, (CO)(PPh3), (CO)(PMe3)) were prepared from
the photochemical reactions of [CpFe(CO)2]2(µ-CHd
CHCHdCH) with dppm, PPh3, and PMe3, respectively.13
The route reported here provides an alternative and
probably more versatile route to C4H4-bridged bimetallic
complexes.35
R ea ct ion s of [R u Cl(CO)(NH 3)(P P h 3)2]2(µ-CH d
CHCHdCH) an d [Ru Cl(CO)(P P h3)2]2(µ-CHdCHCHd
CH) w ith P Et3 a n d t-Bu NC. To obtain more soluble
C4H4-bridged bimetallic complexes, we have tried to
replace the PPh3 and NH3 ligands in complexes 5 and
6 with PEt3 or t-BuNC (Scheme 3). As expected, both
Complex 5 reacted with t-BuNC to give the diacyl-
bridged complex {[Ru(t-BuNC)3(PPh3)2]2(µ-COCHd
CHCHdCHCO)}Cl2 (8A). Similar mononuclear ruthe-
nium complexes such as [Ru(COR)(t-BuNC)3(PPh3)2]+
and [Ru(COR)(t-BuNC)2(CO)(PMe2Ph)2]+ are known.36,37
Interestingly, although RuCl(CHdCHR)(CO)(R′NC)-
(PPh3)2 can be prepared from the reaction of RuCl(CHd
CHR)(CO)(PPh3)2 with R′NC,36 our attempts to prepare
the neutral isocyanide adduct [RuCl(CO)(t-BuNC)-
(PPh3)2]2(µ-CHdCHCHdCH) were unsuccessful. The
presence of the linear C6H4O2 group in complex 8A is
supported by the 13C NMR spectrum (in CD2Cl2), which
showed an Ru-acyl signal at 256.6 ppm, a COCH signal
at 147.3 ppm, and the other CH signal at 124.3 ppm.
For comparison, the 13C signals for the acyl carbon
signal was observed at 260.5 ppm37 for [Ru(COPh)(t-
BuNC)2(CO)(PMe2Ph)2]+ and at 258.1 ppm36 for [Ru-
(COCHdCHCMe3)(t-BuNC)3(PPh3)2]+. Complex 8A is
air stable, and the counteranion Cl- can be readily
replaced with BPh4- to give complex 8B. Complex 8 is
a rare example of a conjugated diacyl bimetallic com-
plex. [CpFe(CO)2]2(µ-OCArCO) is an example of a
reported diacyl-bridged complex, prepared by the reac-
tion of [CpFe(CO)2]- with ClOCArCOCl.38
(32) Touchard, D.; Haquette, P.; Guesmi, S.; Le Pichon, L.; Daridor,
A.; Toupet, L.; Dixneuf, P. H. Organometallics 1997, 16, 3640.
(33) Rappert, T.; Yamamoto, A. Organometallics 1994, 13, 4984.
(34) Ashe, A. J ., III; Mahmoud, S. Organometallics 1988, 7, 1878.
(35) For recent work on insertion reactions of alkynes into M-H
bonds, see for example: (a) Bohanna, C.; Callejas, B.; Edwards, A. J .;
Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C.
Organometallics 1998, 17, 373. (b) Bassetti, M.; Casellato, P.; Gamasa,
M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Mart´ın-Vaca, B. Organo-
metallics 1997, 16, 5470. (c) Wilhelm, T. E.; Belderrain, T. R.; Brown,
S. N.; Grubbs, R. H. Organometallics 1997, 16, 3867. (d) Antin˜olo, A.;
Carroillo-Hermosillia, F.; Fajardo, M.; Garcˆıa-Yuste, S.; Lanfranchi,
M.; Otero, A.; Pellinghelli, M. A.; Prashar, S.; Villasen˜or, E. Organo-
metallics 1996, 15, 5507, and references therein. (e) Chin, C. S.; Lee,
H.; Oh, M. Organometallics 1997, 16, 816. (f) Esteruelas, M. A.; Lahoz,
F. J .; On˜ate, E.; Oro, L. A.; Rodrˆıguez, L. Organometallics 1996, 15,
3670. (g) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier,
B. Organometallics 1994, 13, 4258. (h) Esteruelas, M. A.; Lahoz, F. J .;
On˜ate, E.; Oro, L. A.; Zeier, B. Organometallics 1994, 13, 1662.
Descr ip t ion of t h e St r u ct u r e of [R u Cl(CO)-
(P Et3)3]2(µ-CHdCHCHdCH) (7). The molecular struc-
ture of complex 7 is shown in Figure 1. The crystallo-
(36) Montoya, J .; Santo, A.; Lo`pez, J .; Echavarren, A. M.; Ros, J .;
Romero, A. J . Organomet. Chem. 1992, 426, 383.
(37) Dauter, Z.; Mawby, R. J .; Reynolds, C. D.; Saunders: D. R.;
Hansen, L. K. J . Chem. Soc., Dalton Trans. 1987, 27.
(38) Hunter, A. D.; Ristic-Petrovic, D.; McLernon, J . L. Organome-
tallics 1992, 11, 864.

4766 Organometallics, Vol. 17, No. 22, 1998
Xia et al.
and shorter than the Ru-P bond trans to a vinyl ligand
in RuH(CHdCMeCO2Bu)(CO)(PPh3)3.40 It is noted that
many meridional tris(phosphines)ruthenium complexes
(for example, RuH(OAc)(PPh3)3,41a RuCl2(PPh3)341b) have
mutually trans Ru-P bonds longer than the unique
Ru-P bond.
The two ruthenium centers are bridged symmetrically
by a C4H4 ligand. The C4H4 ligand showed a single
(1.44(1) Å)/double (1.34(2) Å) carbon-carbon bond al-
ternation. The vinyl ligand has a trans configuration.
The Ru-C(vinyl) bond distance of 2.088(8) Å is within
the range reported for ruthenium vinyl complexes, for
example, RuCl(CHdCH-R)(CO)(Me2Hpz)(PPh3)2 (R )
C3H7, (2.05(1) Å;42 R ) CMe3, 2.063(7) Å;43 Me2Hpz )
3,5-dimethylpyrazole), [Ru(Me2OCCdCHCO2Me)(CO)-
(CH3CN)2(PPh3)2]+ (2.12(5) Å),44 TpRu(C(CtCPh)d
CHPh)(CO)(PPh3) (2.090(12) Å),45 and RuCl(PhCdCH-
Ph)(CO)(PPh3)2 (2.03 (1) Å).23a The C-C bond distances
of the C4H4 unit are very similar to that of [CpFe(CO)2]2-
(µ-CHdCHCHdCH).12b
In summary, reaction of Me3SiCtCCtCSiMe3 with
RuHCl(CO)(PPh3)3 gives the mononuclear complex RuCl-
(η1-C(CtCSiMe3)dCHSiMe3)(CO)(PPh3)2. In contrast,
reaction of HCtCCtCH with RuHCl(CO)(PPh3)3 af-
forded a bimetallic complex with a linear C4H4 bridge
that can be converted into a diacyl bridge (COC4H4CO)
by CO insertion.
F igu r e 1. Molecular structure for [RuCl(CO)(PEt3)3]2(µ-
CHdCHCHdCH). Hydrogen atoms are omitted for clarity.
Ta ble 1. Cr ysta l Da ta a n d Refin em en t Deta ils for
[Ru Cl(CO)(P Et3)3]2(µ-CHdCHCHdCH)
formula
fw
C49H94Cl2O2P6Ru2
1096.09
color and habit
crys syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
yellow rectangle
monoclinic
P21/a
14.293(6)
12.576(3)
15.257(3)
90.00(2)
99.19(3)
90.00(3)
2707.3(1)
2
1.337
Z
d
calc, g cm-3
abs coeff, mm-1
F(000)
17.001
2152
Exp er im en ta l Section
radiation (Mo KR), Å
2θ range, deg
scan type
λ ) 0.071 073
Microanalyses were performed by M-H-W Laboratories
(Phoenix, AZ). 1H and 13C NMR chemical shifts are relative
to TMS, and 31P NMR chemical shifts are relative to 85% H3-
PO4.
2.7-50.0
ω-2θ
index range
0 e h e 17
0 e k e 14
-18 e l e 18
5189
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).
reflns collected
ind reflns
obsd reflns
abs correction
max. and min. transmission
quantity minimized
final R indices (obs data)
4996 (Rint ) 0.017)
2823 (F g 3σ(F))
semiempirical
0.9989 and 0.9046
3529 (F g 4σ(F))
R ) 5.3%
Rw ) 6.4%
R ) 6.1%
Rw ) 6.7%
1.201
46
The compound RuHCl(CO)(PPh3)3 was prepared according
to a literature method. All other reagents were used as
purchased from Aldrich or Strem, USA.
Ru Cl(η1-C(CtCSiMe3)dCHSiMe3)(CO)(P P h 3)2 (2). To a
suspension of RuHCl(CO)(PPh3)3 (0.50 g, 0.53 mmol) in 50 mL
of CH2Cl2 was added Me3SiCtCCtCSiMe3 (1.02 g, 5.25 mmol).
The reaction mixture was stirred overnight to give an orange-
brown solution. The volume of the reaction mixture was then
reduced to ca. 5 mL under vacuum. Addition of hexane (100
mL) to the reaction mixture produced a yellow solid, which
was collected by filtration, washed with hexane (30 mL), and
then dried under vacuum. Yield: 0.41 g, 88%. 31P{1H} NMR
(CDCl3, 121.5 MHz): δ 33.3 (s). 1H NMR (CDCl3, 300.13
MHz): δ 0.15 (s, 9 H, SiMe3), 0.22 (s, 9 H, SiMe3), 5.23 (s, 1 H,
dCH), 7.39-7.73 (m, 30 H, 2 PPh3). 13C{1H} NMR (CDCl3,
75.5 MHz): δ -1.1 (s, SiMe3), 0.8 (s, SiMe3), 98.8 (s, tCSiMe3),
114.5 (s, tC), 127.8 (t, J (PC) ) 4.9 Hz, m-Ph), 129.8 (s, p-Ph),
131.9 (t, J (PC) ) 22.2 Hz, ipso-Ph), 134.6 (t, J (PH) ) 5.7 Hz,
o-Ph), 143.1 (s, dCH), 152.6 (t, J (PC) ) 8.4 Hz, Ru-Cd), 207.6
R indices (all data)
goodness of fit
data-to-parameter ratio
largest diff peak, e Å-3
largest diff hole, e Å-3
15.668:1
0.573
-0.071
graphic details and selected bond distances and angles
are given in Tables 1 and 2, respectively. The geometry
around ruthenium can be described as a distorted
octahedron with three meridionally bound PEt3 ligands
and the vinyl group trans to the unique PEt3 ligands,
as indicated by the solution NMR spectroscopic data.
The distortion could be attributed to the steric interac-
tion of the PEt3 ligands as reflected in the P(2)-Ru-
P(1) (99.96(9)°) and P(2)-Ru-P(3) (97.9(1)°) angles. The
unique Ru-P bond (2.440(3) Å) is slightly longer than
those of the mutually trans Ru-P bonds (2.400(2) and
2.397(3) Å), probably due to the strong trans influence
of the vinyl ligand in complex 7. For comparison, the
mutually trans Ru-P bonds are also shorter than the
Ru-P bond trans to a hydride in [RuH(PMe2Ph)5]+ 39
(40) Komiya, S.; Ito, T.; Cowie, M.; Yamamoto, A.; Ibers, J . A. J .
Am. Chem. Soc. 1976, 98, 3874.
(41) (a) Skapski, A. C.; Stephens, F. A. J . Chem. Soc., Dalton Trans.
1974, 390. (b) La Placa, S. J .; Ibers, J . A. Inorg. Chem. 1965, 4, 778.
(42) Torres, M. R.; Santos, A.; Perales, A.; Ros, J . J . Organomet.
Chem. 1988, 353, 221.
(43) Remero, A.; Santos, A.; Vegas, A. Organometallics 1988, 7, 1988.
(44) Lo`pez, J .; Romero, A.; Santos, A.; Vegas, A.; Echavarren, A.
M.; Noheda, P. J . Organomet. Chem. 1989, 373, 249.
(45) Alcock, N. W.; Hill, A. F.; Melling, R. P. Organometallics 1991,
10, 3898.
(39) Ashworth, T. V.; Nolte, M. J .; Singleton, E. J . Chem. Soc.,
Dalton Trans. 1977, 1916.

Bimetallic Ruthenium Complexes
Organometallics, Vol. 17, No. 22, 1998 4767
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles (d eg) for [Ru Cl(CO)(P Et3)3]2(µ-CHdCHCHdCH)
Bond Lengths (Å)
Ru-Cl
Ru-P(3)
C(3)-O
2.484(2)
2.397(3)
1.13(1)
Ru-P(1)
Ru-C(1)
C(1)-C(2)
2.400(2)
2.088(8)
1.34(2)
Ru-P(2)
Ru-C(3)
C(2)-C′(2)
2.440(3)
1.834(9)
1.44(1)
Bond Angles (deg)
Cl-Ru-P(1)
87.52(9)
Cl-Ru-P(2)
91.74(8)
Cl-Ru-P(3)
86.4(1)
99.96(9)
93.1(3)
89.6(2)
89.9(3)
Cl-Ru-C(1)
P(1)-Ru-P(3)
P(2)-Ru-P(3)
P(3)-Ru-C(1)
Ru-C(1)-C(2)
88.8(2)
161.26(9)
97.9(1)
81.2(2)
132.0(6)
Cl-Ru-C(3)
178.9(2)
81.0(2)
178.9(2)
92.6(2)
126(1)
P(1)-Ru-P(2)
P(1)-Ru-C(3)
P(2)-Ru-C(3)
C(1)-Ru-C(3)
P(1)-Ru-C(1)
P(2)-Ru-C(1)
P(3)-Ru-C(3)
C(1)-C(2)-C′(2)
(t, J (PC) ) 16.0 Hz, Ru-CO). IR (KBr, cm-1): ν(CtC) 2094
(w), ν(CO) 1924 (s). Anal. Calcd for C47H49ClOP2Si2Ru: C,
63.82; H, 5.58. Found: C, 63.52; H, 5.57.
CH) and J (AB) ) 15.3, J (AA′) ) 10.0, and J ((BX) ) 2 Hz. IR
(KBr, cm-1): ν(N-H) 3374 (m), ν(CO) 1914 (s). Anal. Calcd
for C78H70Cl2N2O2P4Ru2: C, 63.98; H, 4.82; N, 1.91. Found:
C, 63.71; H, 4.98; N, 1.88.
Ru Cl(η1-C(CtCSiMe3)dCHSiMe3)(CO)(P P h 3)(dppe) (3).
To a solution of complex 2 (0.20 g, 0.23 mmol) in 10 mL of
dichloromethane was added dppe (0.090 g, 0.23 mmol). The
reaction mixture was stirred at room temperature for 20 min
to give a pale green solution. The volume of the reaction
mixture was then reduced to ca. 2 mL under vacuum. Addition
of hexane (30 mL) to the reaction mixture produced a white
solid. The solid was collected by filtration, washed with
hexane, and dried under vacuum. Yield: 0.21 g, 91%. 31P-
{1H} NMR (CDCl3, 121.5 MHz): δ 45.5 (d, J (PP) ) 307.7 Hz,
PPh2), 32.4 (d, J (PP) ) 16.5 Hz, PPh2), 30.2 (dd, J (PP) ) 307.7,
16.5 Hz, PPh3). 1H NMR (CDCl3, 300.13 MHz): δ 0.22 (s, 9
H, SiMe3), 0.89 (s, 9 H, SiMe3), 2.0-3.0 (m, 4 H, CH2), 6.10 (d,
J (PH) ) 1.1 Hz, 1 H, dCH), 7.0-8.0 (m, 35 H, Ph). 13C{1H}
NMR (CD2Cl2, 75.5 MHz): δ -1.0 (s, SiMe3), -0.2 (s, SiMe3),
26.8 (dd, J (PC) ) 28.1, 15.3 Hz, PCH2), 30.8 (m, PCH2), 99.5
(s, tCSiMe3), 118.2 (s, Ct), 126.7-136.3 (m, Ph), 152.7 (dm,
J (PC) ) 60.9 Hz, Ru-CdC), 153.0 (s, dCHSiMe3), 202.3 (td,
J (PC) ) 12.7, 9.1 Hz, Ru-CO). IR (KBr, cm-1): ν(CtC) 2111
(m), ν(CO) 1930 (s). Anal. Calcd for C55H58ClOP3Si2Ru: C,
64.72; H, 5.73. Found: C, 64.46; H, 5.85.
Ru HCl(CO)(NH3)(P P h 3)2 (4). To a suspension of RuHCl-
(CO)(PPh3)3 (0.20 g, 0.21 mmol) in 30 mL of THF was added
NH4F (0.10 g, 2.70 mmol). The reaction mixture was stirred
overnight at room temperature to give a pale green solution.
The volume of the reaction mixture was then reduced to ca. 2
mL under vacuum. Addition of ether (30 mL) to the reaction
mixture produced a white solid, which was collected by
filtration, washed with methanol (10 mL), hexane (10 mL),
and ether (10 mL), and then dried under vacuum. Yield: 0.12
g, 81%. 31P{1H} NMR (CDCl3, 121.5 MHz): δ 46.6 (s). 1H
NMR (CDCl3, 300.13 MHz): δ -14.50 (t, J (PH) ) 18.0 Hz, 1
H, Ru-H), 0.78 (s, 3 H, NH3), 7.41-7.82 (m, 30 H, 2 PPh3).
Anal. Calcd for C37H34ClNOP2Ru‚2H2O‚0.5NH3: C, 59.12; H,
5.30; N, 2.80. Found: C, 59.20; H, 5.20; N, 2.70.
[Ru Cl(CO)(P P h 3)2]2(µ-CHdCHCHdCH) (6). A Schlenk
flask containing RuHCl(CO)(PPh3)3 (2.00 g, 2.10 mmol) sus-
pended in 20 mL of CH2Cl2 was connected to another Schlenk
flask containing Me3SiCtCCtCSiMe3 (1.0 g, 5.1 mmol), H2O
(0.5 mL), and THF (10 mL). The latter flask was heated to
ca. 70 °C, followed by slow addition of n-Bu4NF solution (1.0
mmol in 20 mL of THF) from a dropping funnel with a
dropping rate of ca. 1 mL/min. The volatile contents (presum-
ably, HCtCCtCH, THF) in the second flask were introduced,
in the form of vapor generated by heating, to the flask
containing RuHCl(CO)(PPh3)3. The suspension of RuH-
Cl(CO)(PPh3)3 in CH2Cl2 changed to a reddish-brown suspen-
sion when most of the THF was evaporated. The volume of
the yellow solution was then reduced to ca. 10 mL under
vacuum. The solid was collected by filtration, washed with
ether (20 mL) and acetone (30 mL), and then dried under
vacuum. Yield: 1.1 g, 71%. 31P{1H} NMR (CDCl3, 121.5
MHz): δ 28.3 (s). 1H NMR (CDCl3, 300.13 MHz): δ 5.20 (d,
J (HH) ) 11.0 Hz, 2 H, â-CH), 6.94-7.73 (m, 62 H, 2 Ru-CH,
4 PPh3). IR (KBr, cm-1): ν(CO) 1926 (s). Anal. Calcd for
C78H64Cl2O2P4Ru2: C, 65.50; H, 4.51. Found: C, 65.06; H, 4.79.
[Ru Cl(CO)(P Et3)3]2(µ-CHdCHCHdCH) (7). To a sus-
pension of complex 4 (0.300 g, 0.205 mmol) in 5 mL of CH2Cl2
was added 2.5 mL of a THF solution of PEt3 (1.0 M, 2.5 mmol).
The reaction mixture was stirred for 30 min to give a colorless
solution. Addition of 50 mL of Et2O to the reaction mixture
produced a white solid. The solid was collected by filtration,
washed with ether, and dried under vacuum. Yield: 0.18 g,
81%. 31P{1H} NMR (CDCl3, 121.5 MHz, -20 °C): δ 0.6 (t,
J (PP) ) 19.3 Hz), 5.8 (d, J (PP) ) 19.3 Hz). 1H NMR (CD2Cl2,
300.13 MHz, -20 °C): δ 1.00-1.15 (m, 54 H, CH3), 1.79-1.88
(m, 36 H, CH2), 6.22 (m, 2 H, Ru-CHdCH), 6.64 (m, 2 H, Ru-
1
CHdCH). The 31P and H NMR spectra were recorded at -20
1
°C because the 31P and H signals are somewhat broad at room
temperature. 13C{1H} NMR (CD2Cl2, 75.5 MHz): 7.6 (s, CH3),
8.23 (d, J (PC) ) 2.7 Hz, CH3), 17.1 (t, J (PC) ) 12.7 Hz, CH2),
19.2 (d, J (PC) ) 15.1 Hz, CH2), 144.7 (s, Ru-CHdCH), 151.6
(brd, J (PC) ) 74.4 Hz, Ru-CH), 204.1 (q, J (PC) ) 13.4 Hz,
[R u Cl(CO)(NH 3)(P P h 3)2]2(µ-CH dCH CH dCH ) (5).
A
Schlenk flask containing RuHCl(CO)(PPh3)3 (3.00 g, 3.15
mmol) suspended in 50 mL of CH2Cl2 was connected to another
Schlenk flask containing Me3SiCtCCtCSiMe3 (1.0 g, 5.1
mmol), NH4F (1.0 g, 27 mmol), n-Bu4NF on silica gel (1.0 g,
1.1 mmol F-), H2O (0.5 mL), and THF (10 mL). The volatile
contents (presumably, HCtCCtCH, THF, NH3) in the second
flask were then introduced, in the form of vapor generated by
heating (at ca. 70 °C), to the flask containing RuHCl(CO)-
(PPh3)3. The suspension of RuHCl(CO)(PPh3)3 in CH2Cl2
changed into a clear yellow solution when most of the THF
was evaporated (ca. 2 h). The volume of the yellow solution
was then reduced to ca. 10 mL under vacuum, and 200 mL of
ether was added to give a yellow solid. The solid was collected
by filtration, washed with ether (30 mL) and small amount of
CH2Cl2, and then dried under vacuum. Yield: 1.2 g, 52%. 31P-
{1H} NMR (CDCl3, 121.5 MHz): δ 37.8 (s). 1H NMR (CDCl3,
300.13 MHz): δ 0.86 (s, 6 H, 2 NH3), 7.21-7.73 (m, 60 H, 4
PPh3). The C4H4 unit showed an AA′BB′XX′ (X ) PPh3)
pattern with δA ) 4.63 (Ru-CHdCH), δB ) 5.89 ppm (Ru-
CO). IR (KBr, cm-1): ν(CO) 1904 (s). Anal. Calcd for C42H94
-
Cl2O2P6Ru2: C, 46.28; H, 8.69; Cl, 6.50. Found, 45.99; H, 8.43;
Cl, 6.66.
{[R u (t-Bu NC)3(P P h 3)2]2(µ-COCHdCHCHdCHCO)}Cl2
(8A). To a suspension of complex 4 (0.200 g, 0.137 mmol) in
20 mL of dichloromethane was added t-BuNC (0.20 mL, 1.8
mmol). The reaction mixture was stirred at room temperature
overnight to give an orange-red solution. The volume of the
reaction mixture was then reduced to ca. 2 mL under vacuum.
Addition of 30 mL of hexane to the reaction mixture produced
a red solid. The solid was collected by filtration, washed with
hexane, and dried under vacuum. Yield: 0.22 g, 83%. 31P-
{1H} NMR (CDCl3, 121.5 MHz): δ 36.1 (s). 1H NMR (CDCl3,
300.13 MHz): δ 1.02 (s, 4 t-BuNC), 1.06 (s, 2 t-BuNC), 7.36-
7.51 (m, Ph). The C4H4 unit showed an AA′BB′ pattern with
δA ) 4.93, δB ) 6.04 (CO-CH) ppm and J (AB) ) 13.8, J (AA′)

4768 Organometallics, Vol. 17, No. 22, 1998
Xia et al.
) 12.0 Hz. 13C{1H} NMR (CD2Cl2, 75.5 MHz): δ 29.2 (s,
CMe3), 29.3 (s, CMe3), 57.6 (s, CMe3), 57.7 (s, CMe3), 124.3 (s,
COCHdCH), 128.1 (t, J (PC) ) 4.7 Hz, m-Ph), 130.2 (s, p-Ph),
133.6 (t, J (PC) ) 5.3 Hz, o-Ph), 134.0 (t, J (PC) ) 22.3 Hz, ipso-
Ph), 146.4 (br, Ru-CN), 147.3 (s, CO-CHdCH), 148.3 (brt,
J (PC) ) 13.2 Hz, Ru-CN), 256.6 (t, J (PC) ) 9.4 Hz, Ru-CO).
IR (KBr, cm-1): ν(CtN) 2140 (s), ν(CdO) 1630 (br, m). Anal.
Calcd for C108H118Cl2O2N6P4Ru2‚5H2O: C, 64.24; H, 6.39.
Found, C, 64.39; H, 6.27.
{[R u (t -Bu NC)3(P P h 3)2]2(µ-COCH dCH CH dCH CO)}-
(BP h 4)2. (8B). To a solution of complex 8A (0.20 g, 0.10
mmol) in 20 mL of CH2Cl2 was added NaBPh4 (0.40 g, 1.2
mmol). The reaction mixture was stirred at room temperature
for 20 min to give an orange solution. The volume of the
reaction mixture was reduced to ca. 2 mL under vacuum.
Addition of hexane (30 mL) produced an orange solid, which
was collected by filtration, washed with methanol (10 mL) and
hexane (10 mL), and then dried under vacuum. Yield: 0.25
used for structure solution and refinement using the Nonius
MolEN program package.47 Solution by direct methods yielded
the positions of all non-hydrogen atoms. Refinement by full-
matrix least-squares resulted in final discrepancy indices R
) 5.3%, Rw ) 6.4% with GOF ) 1.201. All non-hydrogen atoms
were refined with anisotropic thermal parameters. All hy-
drogens were revealed in difference Fourier maps, but then
placed geometrically determined positions with dC-H ) 0.96
Å and refined isotropically with riding constraints and group
thermal parameters. The data:parameter ratio was 15.668:
1, and residual electron density/hole +0.573/-0.071 e Å-3
.
Further crystallographic details and selected bond distances
and angles are given in Tables 1 and 2, respectively.
Ack n ow led gm en t. The authors acknowledge finan-
cial support from the Hong Kong Research Grants
Council and thank Mr. J ingzhi Wang for his technical
support in the crystallographic determination.
g, 95%. The NMR data are essentially the same as those of
complex 8A, except the additional 1H and 13C signals of BPh4
.
-
Anal. Calcd for C156H158B2O2N6P4Ru2: C, 75.05; H, 6.38.
Found: C, 74.86; H, 6.38.
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, anisotropic
displacement coefficients, and positional and thermal param-
eter for hydrogen for [RuCl(CO)(PEt3)3]2(µ-CHdCHCHdCH)
(6 pages). Ordering information is given on any current
masthead page.
Cr ysta llogr a p h ic An a lysis for [Ru Cl(CO)(P Et3)3]2(µ-
CHdCHCHdCH) (7). Suitable crystals for X-ray diffraction
study were obtained by slow diffusion of ether to a CH2Cl2
solution saturated with complex 7. A specimen of dimension
0.22 × 0.25 × 0.44 mm3 was mounted on a glass fiber and
used for X-ray structure determination. The diffraction data
were collected on a Enraf/Nonius CAD4-VAX/2100 X-ray
diffractometer at 293 K. The crystal system was monoclinic
with space group P21/a. A total of 5189 intensity measure-
ments were made using the 2θ-θ scan technique in the range
2.7° e 2θ e 50° (Mo KR radiation). Of these, 4996 were unique
(Rint ) 1.7%) and 3529 observed with F ) 4σ(F), which were
OM9804935
(46) Ahmad, N.; Levison, J . J .; Robinson, S. D.; Uttley, M. F.;
Wonchoba, E. R.; Parshall, G. W. Inorg. Synth. 1974, 15, 45.
(47) Fair, C. K. MolEN An Interactive Interlligent System for Crystal
Structure Analysis; Enraf-Nonios: Delft, The Netherlands, 1990.