Preparation of dinuclear vinylidene complexes and their new deprotonation reactions

Article abstract of DOI:10.1021/om060641o

The dinuclear dicationic vinylidene complex {[Ru]=C-C(Ph)CH ₂C(CH₂CN)=C=[Ru]}²⁺ (7a, [Ru] = Cp(PEt ₃)₂Ru) is prepared from the reaction of ICH₂CN with {[Ru]=C=C(Ph)CH₂C≡C[Ru]}⁺ (6a). Deprotonation of 7a by n-Bu₄NOH is followed by a cyclization process yielding the stable complex 9a, containing a five-membered carbocyclic ring ligand, which is fully characterized by 2D-NMR analysis and a single-crystal X-ray diffraction analysis. Similarly deprotonation of {[Ru]=C=C(Ph)CH₂C(CH ₂-COOEt)=C=[Ru]}²⁺ (8a) gave the stable product lia containing a bridging ligand also with a similar five-membered carbocyclic ring. The cyclization process is affected by an ancillary ligand on the Ru metal center. Thus the analogous dinuclear complex 9b, with a bistriphenylphosphine ligand on one metal, which is prepared in a similar manner from {[Ru]=C=C(Ph)CH₂C(CH₂CN)=C=[Ru′]}²⁺ (7b, [Ru′] = Cp(PPh₃)₂Ru), is unstable, undergoing isomerization to give the dinuclear complex 10b, containing a cyclopropenyl ligand.

Full text of DOI:10.1021/om060641o

Organometallics 2007, 26, 3431-3439
3431
Preparation of Dinuclear Vinylidene Complexes and Their New
Deprotonation Reactions
Chung-Wei Liu, Ying-Chih Lin,* Shou-Ling Huang, Cheng-Wei Cheng, Yi-Hung Liu, and
Yu Wang
Department of Chemistry, National Taiwan UniVersity, Taipei, Taiwan 106, Republic of China
ReceiVed July 17, 2006
The dinuclear dicationic vinylidene complex {[Ru]dCdC(Ph)CH2C(CH2CN)dCd[Ru]}2+ (7a, [Ru]
) Cp(PEt3)2Ru) is prepared from the reaction of ICH2CN with {[Ru]dCdC(Ph)CH2CtC[Ru]}+ (6a).
Deprotonation of 7a by n-Bu4NOH is followed by a cyclization process yielding the stable complex 9a,
containing a five-membered carbocyclic ring ligand, which is fully characterized by 2D-NMR analysis
and a single-crystal X-ray diffraction analysis. Similarly deprotonation of {[Ru]dCdC(Ph)CH2C(CH2-
COOEt)dCd[Ru]}2+ (8a) gave the stable product 11a containing a bridging ligand also with a similar
five-membered carbocyclic ring. The cyclization process is affected by an ancillary ligand on the Ru
metal center. Thus the analogous dinuclear complex 9b, with a bistriphenylphosphine ligand on one
metal, which is prepared in a similar manner from {[Ru]dCdC(Ph)CH2C(CH2CN)dCd[Ru′]}2+ (7b,
[Ru′] ) Cp(PPh3)2Ru), is unstable, undergoing isomerization to give the dinuclear complex 10b, containing
a cyclopropenyl ligand.
unsaturated carbon-rich ligands such as acetylide, vinylidene,
and allenylidene have focused more or less on the electron-
transfer phenomena mediated by a conjugated bridging ligand.11
A collection of linkers such as conjugated carboxylates,12
polyaromatics,11 polyynes,13-15 polyenes,16 or polypyridyl com-
plexes17 have been used for prospective applications such as
molecular wires,18 dyes,19 unusual magnetic20 or nonlinear
optical21 properties, and quantum cell automata.22 We previously
reported the synthesis of a number of mononuclear ruthenium
cyclopropenyl complexes23 by a deprotonation reaction of
readily accessible ruthenium vinylidene complexes containing
Introduction
The stabilization of vinylidene1 upon coordination to a metal
center2 is now a common feature experienced with many
transition metals, and chemical properties of metal vinylidene
complexes3 are valuable for novel organic transformations. For
example formation of a metal vinylidene intermediate4 has been
used to promote various carbon-carbon bond forming reactions
by the addition of a nucleophilic carbon center to the electro-
philic vinylidene R-carbon atom. Vinylidene complexes of
various metals also function as strategic intermediates5 for the
catalytic conversion of alkynes such as cycloaromatization of
conjugated enediynes,6 the dimerization of terminal alkynes,7
and the addition of oxygen, nitrogen, and carbon nucleophiles
to alkynes.8 Therefore the synthesis and reactivity of these
unsaturated ligands, particularly the ruthenium vinylidene
system,9 are nevertheless under active investigation.10 While the
reactivity of mononuclear vinylidene complexes finds their
applications, studies on dinuclear metal complexes with highly
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* Corresponding author. E-mail: yclin@ntu.edu.tw.
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10.1021/om060641o CCC: $37.00 © 2007 American Chemical Society
Publication on Web 06/02/2007

3432 Organometallics, Vol. 26, No. 14, 2007
Liu et al.
a -CH2R group bound to Câ of the vinylidene ligand. In a
slightly different vinylidene system containing a pendant -CPh2-
CH2CHdCH2 group bound to Câ of the vinylidene ligand, the
ruthenium vinylidene complex displays novel intramolecular
metathesis reactivity between the two CdC double bonds.24
Encouraged by the rich chemistry of ruthenium vinylidene
complexes, we set to explore the chemical reactivity of dinuclear
bisvinylidene complexes. Since relatively few dinuclear com-
plexes with an odd-numbered carbon bridge have been ob-
tained,25,26 we therefore started with dinuclear complexes with
an unsaturated five-carbon bridge. Herein we report the synthesis
of dinuclear vinylidene complexes of ruthenium and osmium
and their novel deprotonation reactions.
Results and Discussion
Synthesis of Dinuclear Ruthenium Vinylidene Complexes.
The reported preparation of ruthenium acetylide complexes27
is modified to obtain [M]-CtC-Ph (3a, [M] ) Cp(PEt3)2Ru;
3c, [M] ) Cp(PPh3)2Os) in high yield. Treatment of [M]-Cl
(1a, [M] ) Cp(PEt3)2Ru) with phenylacetylene in the presence
of KPF6 in methanol afforded {[M]dCdC(H)Ph}PF6 (2a, [M]
) Cp(PEt3)2Ru), and then deprotonation of 2a by MeONa
yielded complex 3a as a yellow solid. Complex 3c was similarly
obtained from Cp(PPh3)2OsCl (1c). Alkylations of acetylide
complexes 3a and 3c readily gave vinylidene complexes. Thus,
the reaction of 3a with HCtCCH2Br in the presence of KPF6
yields the air-stable cationic vinylidene complex {[Ru]dCd
C(Ph)CH2CtCH}PF6 (4a) in high yield. Similarly the osmium
complex 4c was obtained. Spectroscopic data of 4a including
1H, 31P{1H}, and 13C{1H} NMR spectra clearly reveal the
presence of the vinylidene moiety. For example, in the 13C NMR
spectrum of 4a, the typical downfield resonance of CR appears
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2
as a triplet at δ 345.92 with JCP ) 14.7 Hz. The terminal
alkynyl group of 4a further reacted with [Ru]-Cl to give the
bisvinylidene complex 5a, which upon deprotonation gave the
alkynyl vinylidene complex {[Ru]dCdC(Ph)CH2CtC-[Ru]}-
PF6 (6a, [Ru] ) Cp(PEt3)2Ru) in the presence of base. Complex
6a contains a methylene bridge between the metal vinylidene
and the metal acetylide fragments. Similarly complex {[Ru]d
CdC(Ph)CH2CtC-[Ru′]}PF6 (6b, [Ru′] ) Cp(PPh3)2Ru) was
isolated from the reaction of 4a and Cp(PPh3)2RuCl (1b) in high
yield also via 5b; see Scheme 1.
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Spectroscopic data support the description of 5a, 5b, 6a, and
6b. Interestingly, in the 13C NMR spectrum of 5a, three typical
downfield triplet resonances of CR are observed at δ 344.76
2
2
with JCP ) 15.5 Hz, 344.44 with JCP ) 15.1 Hz, and 343.06
with 2JCP ) 15.1 Hz, with the former two showing half intensity.
The 31P NMR spectrum also displays one singlet signal at δ
37.50 and two singlet resonances with half intensity at 38.89
1
and 38.87, and the H NMR spectrum shows a broad peak for
the vinylidene proton. Low-temperature NMR data indicate that
chemical shifts of these resonances are temperature dependent.
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triethylphosphine ligands on the phenyl-substituted vinylidene
portion (with coalescence temperature at 183 K), while the other
two resonances merged into a broad one at δ 39.9, possibly
because of lower resolution at low temperature. It is well known
that vinylidene complexes of the type MdCdCRR′ exhibit
optical isomerism like allenes, however, mostly with a low
barrier for the rotation of the M-vinylidene carbon bond. By
freezing the rotation, one can observe the optical isomerism.
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Preparation of Dinuclear Vinylidene Complexes
Organometallics, Vol. 26, No. 14, 2007 3433
Scheme 1
Figure 1. ORTEP plot of complex 6b drawn at the 30% probability
level. Phenyl groups on the phosphine ligands on Ru(2) have been
omitted for clarity except the C(ipso) atoms.
Table 1. Selected Bond Lengths [Å] and Angles [deg] for
Complex 6b
Ru(1)-C(1)
1.834(5)
1.315(6)
1.463(7)
166.3(4)
119.1(4)
177.2(5)
Ru(2)-C(5)
2.030(5)
1.535(7)
1.201(6)
174.5(4)
112.2(4)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
Ru(2)-C(5)-C(4)
C(2)-C(3)-C(4)
Ru(1)-C(1)-C(2)
C(1)-C(2)-C(3)
C(3)-C(4)-C(5)
6b suitable for X-ray diffraction were grown by slow diffusion
of diethyl ether into a saturated dichloromethane solution. An
ORTEP view of the molecular structure of 6b is shown in Figure
1, with selected bond distances and angles given in Table 1.
X-ray diffraction studies reveal that the dinuclear complex 6b
has vinylidene and acetylide ligands bridged by a methylene
group. The Ru(1)-C(1) and C(1)-C(2) bond lengths of 1.834-
(5) and 1.315(6) Å, respectively, are comparable with the Ru-
vinylidene distances found in other ruthenium complexes.28 The
Ru(2)-C(5) and C(4)-C(5) bond lengths are 2.030(5) and
1.201(6) Å, respectively, and are similar to the distances
observed in other ruthenium acetylide complexes.29 The C(3)-
C(4)-C(5) bond angle measures 177.2(5)° and confirms the
presence of the acetylide ligand on Ru(2). The remaining bond
lengths and angles are normal and lie within the expected range.
Alkylations of the two dinuclear complexes 6a and 6b each
with ICH2CN in CH2Cl2 at room temperature in the presence
of KPF6 afforded bisvinylidene complexes {[M]dCdC(Ph)-
CH2-C(CH2CN)dCd[M′]}[PF6]2 (7a, [M] ) [M′] ) Cp-
(PEt3)2Ru; 7b, [M] ) Cp(PEt3)2Ru, [M′] ) Cp(PPh3)2Ru),
respectively, both as pink powders. The 31P NMR spectrum of
7a displays two singlet resonances at δ 36.39 and 35.47. In the
Particularly for the piano-stool-type cationic ruthenium complex
CpL2RudCdCRR′+ with two identical phosphine ligands, two
coupled doublet resonances in the low-temperature 31P NMR
spectrum show such an isomerism. The fact that at room
temperature the 31P NMR spectrum of 5a shows all singlet
resonances indicates that the rotation of the Ru-vinylidene
group remains fast. Temperature-dependent spectra demonstrate
that only at low temperature is the fluxional process due to the
rotation of the Ru vinylidene group hampered, thus showing
diastereomers. Therefore, at room temperature the three CR
resonances as well as three 31P singlet resonances could possibly
be due to the existence of two conformational isomers in a 1:1
ratio. No such isomer was observed for 5b. For dinuclear
bisvinylidene complexes with no hydrogen on Câ (complexes
7 and 8 described below), neither do we see the existence of
isomers. Thus the existence of isomers seems to require both
the presence of triethylphosphine ligands on the nearby metal
and the hydrogen atom on Câ of the vinylidene ligand. Since a
facile tautomeric interconversion between the vinylidene and
the π-bound alkynyl form is expected for the vinylidene ligand
with a hydrogen atom, our observation of two species in the
NMR spectra could very well be attributed to the presence of
conformational isomers via the facile tautomeric interconversion.
However, if the P-P couplings between phosphine ligands are
negligible, this could be due to the presence of diastereomers.
The 31P{1H} NMR spectrum of 6a exhibits two singlet
resonances at δ 36.03 and 48.99, with the latter one appearing
in the region of the metal acetylide. In the 13C NMR spectrum
of 6a only one downfield triplet resonance at δ 350.44 for CR
of the vinylidene group was observed. These data confirm the
existence of both vinylidene and acetylide groups in 6a.
Addition of base including OH-, F-, DBU, and MeLi to 6a
in acetone at room temperature caused no reaction, indicating
that the methylene group of complex 6a would not undergo
deprotonation reaction. Complex 6a is air-stable and decomposes
in solution at 70 °C. The solid-state structure of 6b is determined
by an X-ray diffraction analysis. Single crystals of the complex
13C NMR spectrum of 7a, typical downfield triplet resonances
2
of CR are observed at δ 339.45 and 338.97, both with JCP
)
14.6 Hz. The corresponding downfield triplet resonances of CR
for 7b appear at δ 342.91 with 2JCP ) 15.2 Hz and at δ 337.96
2
with JCP ) 14.3 Hz. Alkylation of complex 6a with ethyl
iodoacetate in CH2Cl2 in the presence of KPF6 gives the
bisvinylidene complex {[M]dCdC(Ph)CH2C(CH2COOEt)d
Cd[M]}[PF6]2 (8a, [M] ) Cp(PEt3)2Ru). In the 1H NMR
spectrum of 8a, two singlet resonances at δ 3.75 and 3.43 and
one quartet resonance at δ 4.25 are assigned to protons of three
methylene groups. The 31P NMR spectrum of 8a displays two
(28) (a) Hill, A. F.; Hulkes, A. G.; White, A. J. P.; Williams, D. J.
Organometallics 2000, 19, 371. (b) Bruce, M. I.; Ellis, B. G.; Low, P. J.;
Skelton, B. W.; White, A. H. Organometallics 2003, 22, 3184.
(29) (a) Bruce, M. I.; Ellis, B. G.; Gaudio, M.; Lapinte, C.; Melino, G.;
Paul, F.; Skelton, B. W.; Smith, M. E.; Toupet, L.; White, A. H. Dalton
Trans. 2004, 1601. (b) Bruce, M. I.; Hall, B. C.; Kelly, B. D.; Low, P. J.;
Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton Trans. 1999, 3719.

3434 Organometallics, Vol. 26, No. 14, 2007
Liu et al.
Table 2. Selected Bond Lengths [Å] and Angles [deg] for
Complex 9a
Ru(1)-C(1)
2.112(6)
1.350(9)
1.517(9)
1.280(8)
Ru(2)-C(7)
1.854(6)
1.523(9)
1.542(8)
1.557(9)
168.6(6)
103.3(5)
106.0(5)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(7)
Ru(1)-C(1)-C(2)
C(1)-C(2)-C(3)
C(3)-C(4)-C(5)
C(2)-C(1)-C(5)
C(4)-C(5)
C(1)-C(5)
Ru(2)-C(7)-C(4)
C(2)-C(3)-C(4)
C(1)-C(5)-C(4)
133.7(5)
115.6(6)
105.7(5)
105.7(5)
geometry for both Ru centers. The distances Ru(1)-C(1) (2.112-
(6) Å) and Ru(2)-C(7) (1.854(6) Å) agree with that for a single
bond and a double bond, respectively.28 The angle Ru(2)-C(7)-
C(4) of 168.6(6)° involved in the vinylidene group is close to
the ideal value. With respect to the cyclic bonds, C(1)-C(2)
(1.350(9) Å) is clearly a double bond, while the C(1)-C(5)
distance amounts to 1.557(9) Å, in agreement with its single-
bond character. The distance C(1)-C(5), next to the Ru(1)
moiety, is slightly greater than the other three (C(2)-C(3) 1.523-
(9) Å, C(3)-C(4) 1.517(9) Å, C(4)-C(5) 1.542(8) Å) and
reflects the influence of the metal moiety.
Figure 2. ORTEP plot of complex 9a drawn at the 30% probability
level.
Scheme 2
We previously reported that the deprotonation reaction of the
mononuclear vinylidene complex Cp(PPh3)2RudCdC(Ph)CH2-
CN+ gave a ruthenium complex containing an unsaturated three-
membered cyclopropenyl ligand.23b Interestingly, in the dinu-
clear bisvinylidene complex a different cyclization process
resulted in formation of a five-membered carbocyclic ring. For
comparison, the dinuclear complex 7b, with one metal contain-
ing two triphenylphosphine ligands, was reacted with n-Bu4-
NOH in acetone. Interestingly the reaction yielded the yellow
cyclopropenyl product 10b; see Scheme 2. The reaction proceeds
via formation of a visible red intermediate during the reaction
period which could be obtained by replacing the base with
NaOMe. By treating the complex 7b with 5 equiv of NaOMe
in acetone for 30 min, a deep red solution showing the presence
of a mixture of 9b and 10b in a 10:1 ratio was obtained.
Complex 10b is soluble in hexane or ether, but complex 9b is
hexane insoluble and is soluble in CH2Cl2. It is therefore easy
to separate 9b from the mixture. Complex 9b is air-stable and
displays a deep red color in solution but decomposes at about
80 °C. Interestingly, in the absence of base, 9b in acetone is
stable at room temperature, but in the presence of base,
formation of complex 10b is observed. Product 10b could also
be obtained from the deprotonation reaction using NaOMe with
longer reaction time, i.e., when the color of the solution turns
bright yellow. Extraction with ether gave 10b in good yield as
a yellow powder.
singlet resonances at δ 36.47 and 35.58. Complex 8b is also
prepared from 6b and ethyl iodoacetate.
Deprotonation Reactions of Dinuclear Complexes. Treat-
ment of complex 7a with NaOMe or n-Bu4NOH in acetone at
room temperature afforded the air-stable complex 9a (see
Scheme 2) as a deep red powder. Deprotonation of the
methylene protons near the CN group followed by a novel
cyclization leads to a C-C bond formation at CR of the remote
Ru vinylidene group. Complex 9a, containing a stereogenic
carbon center in the five-membered ring, is characterized by
1H, 31P, 13C, 2D-NMR, and MS spectra. The 1H NMR spectrum
of 9a exhibits a set of two doublet resonances at δ 4.42 and
4.21 with 2JHH ) 17.4 Hz corresponding to the gem-methylene
groups. The proton resonance of the methyne group of the five-
membered ring appears as a singlet peak at δ 5.08. The 31P
NMR spectrum of 9a, containing a stereogenic carbon center,
displays two sets of two doublet resonances at δ 39.73 and 37.88
(2JPP ) 32.6 Hz) and 29.77 and 29.36 (2JPP ) 45.9 Hz). The
13C NMR spectrum displays one typical downfield triplet
resonance at δ 339.81 with 2JCP ) 15.0 Hz for CR. Furthermore,
2D NMR data of 9a reveal the presence of the five-membered
1
The H NMR spectrum of complex 9b shows two doublet
2
resonances at δ 4.54 and 4.09 with JHH ) 18.0 Hz for the
methylene group. The proton of the methyne group exists as a
singlet peak at δ 5.05. The 31P NMR spectrum of 9b contains
four doublet resonances at δ 39.73 and 37.88 (2JPP ) 32.6 Hz)
and δ 29.77 and 29.36 (2JPP ) 45.9 Hz). In the 13C NMR
spectrum of 9b the triplet peak at δ 341.46 (2JCP ) 11.8 Hz) is
attributed to the typical CR of the vinylidene ligand. On the
basis of these spectroscopic data the structure of 9b is analogous
1
1
carbocyclic ring. In the H,13C-HMBC spectrum of 9a, cross-
to 9a. The spectroscopic data of 10b, including H, 31P, 13C,
1
peaks between the H resonance of CH at δ 5.08 and 13C
2D-NMR, and MS, are consistent with the structure shown in
1
resonances of other four carbocyclic carbon atoms at δ 149.34,
144.31, 121.38, and 46.26 indicated long-range C-H correla-
tion, inferring formation of the five-membered ring. Unequivocal
characterization of 9a was performed by X-ray structure
analysis. Figure 2 shows an ORTEP representation of the
molecule. Selected bond distances and angles are listed in Table
2. The structure can be described as three-legged piano stool
Scheme 2. For example in the H NMR spectrum of 10b, also
containing a stereogenic carbon center in the three-memberd
2
ring, two doublet resonances at δ 3.53 and 3.46 with JHH
)
16.5 Hz are assigned to the methylene group. The stereogenic
carbon center is close to the metal center with the bistriph-
enylphosphine ligands; therefore the 31P NMR spectrum displays
a singlet peak at δ 35.78 as well as resonances showing an AB

Preparation of Dinuclear Vinylidene Complexes
Organometallics, Vol. 26, No. 14, 2007 3435
pattern at δ 51.07 and 50.68 with 2JPP ) 39.8 Hz assignable to
two PEt3 ligands and two PPh3 ligands, respectively. It is not
possible to convert 9a to the corresponding cyclopropenyl
complex. An electronic effect may play a role in the selectivity
of C-C bond formation.
Concluding Remark
In summary, dinuclear ruthenium and osmium vinylidene
complexes containing bistriethylphosphine or bistriphenylphos-
phine ligands were synthesized. The deprotonation reaction of
the dinuclear bisvinylidene complex 7a was followed by a novel
cyclization reaction with carbon-carbon bond formation be-
tween the deprotonated carbon and CR of the remote vinylidene
ligand, giving the dinuclear complex 9a with a bridging ligand
containing a five-membered carbocyclic ring. The deprotonation
of 7b proceeds via a similar pathway, yielding the parallel
complex 9b. However, complex 9b, with bistriphenylphosphine
ligands, is unstable in the presence of base, generating 10b with
a cyclopropenyl ring. Electronic effects of various phosphine
ligands can possibly control the regiochemistry of C-C bond
formation following deprotonation reactions, leading to various
products. Deprotonation of dinuclear complexes with a triph-
enylphosphine ligand favor formation of a cyclopropenyl product
as a thermodynamic product.
Deprotonation of 8a was similarly carried out in acetone.
From 8a complex 11a was observed in 76% NMR yield. Our
attempts to isolate 11a in pure form were unsuccessful. Even
though pure complex 11a was not obtained, NMR characteriza-
tion indicated that an analogous five-membered carbocyclic ring
appears in the bridging ligand. In the 2D HMBC spectrum of
11a, a long-range C-H correlation was observed between the
proton resonance of CH at δ 4.94 and the four cyclic carbon
resonances at δ 152.80, 144.33, 123.56, and 47.60, indicating
formation of the same five-membered ring as that in 9. The
same long-range coupling pattern was also observed in that of
9a. Attempts to convert 11a either to a cyclopropenyl or furyl
complex led to decomposition. Interestingly, for 8b, with two
triphenylphosphine ligands, the deprotonation using Bu4NOH
gave complex 12b in quantitative NMR yield. We could not
observe any intermediate during this transformation and, again,
failed to isolate complex 12b in pure form. However, in the
31P NMR spectrum of the reaction mixture, the very clean
pattern with two singlet resonances at δ 49.45 and 36.49 clearly
reveals formation of the furyl complex in quantitative yield.
The 31P resonance at δ 49.45 is in the same region as that of
other Ru furyl complexes with a triphenylphosphine ligand.23b
Experimental Section
General Procedures. The manipulations were performed under
an atmosphere of dry nitrogen using vacuum-line and standard
Schlenk techniques. Solvents were dried by standard methods and
distilled under nitrogen before use. All reagents were obtained from
commercial suppliers and used without further purification. Com-
pounds [Ru]Cl (1a, [Ru] ) Cp(PEt3)2Ru), [Ru′]Cl (1b, [Ru′] )
Cp(PPh3)2Ru), [Os]Cl (1c, [Os] ) Cp(PPh3)2Os), and [Os]CtCPh
were prepared by following the methods30 reported in the literature.
Infrared spectra were recorded on a Nicolet-MAGNA-550 spec-
trometer. The C, H, and N analyses were carried out with a Perkin-
Elmer 2400 microanalyzer. Mass spectra (FAB) were recorded using
a JEOL SX-102A spectrometer; 3-nitrobenzyl alcohol (NBA) was
used as the matrix. NMR spectra were recorded on a Bruker AC-
300 instrument (at 300 MHz (1H), 121.5 MHz (31P), or 75.4 MHz
(13C) using SiMe4 or 85% H3PO4 as standard) or on a Bruker
Avance 500 FT-NMR spectrometer.
Synthesis of {[Ru]dCdC(H)Ph}PF6 (2a). To a Schlenk flask
charged with 1a (0.42 g, 0.96 mmol) and KPF6 (0.88 g, 4.80 mmol)
was added methanol (20 mL) under nitrogen. The resulting solution
was stirred at room temperature, and phenylacetylene (1.05 mL,
9.60 mmol) was added. The clear solution was stirred for 1.5 h,
and the color changed from orange to red. After the solvent was
removed under vacuum, 30 mL of CH2Cl2 was added. The solution
was filtered through Celite, and the volume of the solution was
reduced to 5 mL under vacuum. Then 60 mL of diethyl ether was
added to cause precipitation of a pink powder. After filtration, the
precipitate was washed with 10 mL of diethyl ether twice and then
dried under vacuum to give 2a (0.45 g, 72% yield). 1H NMR
(CDCl3): 7.35-6.90 (m, 5H, Ph), 5.54 (s, 5H, Cp), 5.33 (s, 1H,
CâH), 2.05-1.85 (m, 6H, CH2), 1.85-1.65 (m, 6H, CH2), 1.09-
1.00 (m, 18H, CH3). 13C NMR CDCl3: 351.78 (t, 2JCP ) 15.3 Hz,
CR), 128.97-125.94 (Ph), 116.84 (Câ), 90.64 (Cp). 31P NMR
(CDCl3): 36.92 (s, PEt3). MS FAB m/z: 505.1 (M+ - PF6), 403.1
(M+ - PF6 - CdC(H)Ph). Anal. Calcd for C25H41F6P3Ru: C,
46.23; H, 6.36. Found: C, 46.62; H, 6.15.
On the basis of the reactivity of 7a, 7b, 8a, and 8b it could
be concluded that the phosphine ligand may play a key role in
determining the regiochemistry of the cyclization. With a more
electron-donating ability, the triethylphosphine ligand could
direct the C-C bond formation to take place at CR of the remote
vinylidene ligand. For complex 7b, with a triphenylphosphine
ligand, the less ring-strained energy of the five-membered
carbocycle could stabilize the kinetic product 9b, which
eventually transforms to the thermodynamic product 10b. A
series of osmium-ruthenium vinylidene complexes 4c, 5c, 6c,
and 7c all with triphenylphosphine ligands were prepared. The
deprotonation of 7c cleanly and directly gave the cyclopropenyl
complex 10c; see Scheme 2. The reaction did not give the
intermediate with the five-membered-ring bridging ligand. In
this system the regiochemistry of the cyclization could be readily
discriminated by 13C NMR data. Resonances of CR of the
vinylidene ligands for Ru and Os in 7c appear distinctively at
δ 341.51 and 302.24, respectively. The downfield resonance at
δ 307.23 for 10c indicates the presence of an Os vinylidene
moiety, revealing the site of cyclization at CR of the vinylidene
ligand on Ru.
In order to check the feasibility for the formation of a
cyclopropenyl and furyl complex in mononuclear system
containing triethylphosphine ligands, complexes [Ru]dCd
C(Ph)CH2R+ (13, R ) CN; 14, R ) CO2Me; [Ru] ) Cp(PEt3)2-
Ru) are prepared from the reactions of 3a with two organic
halides, ICH2CN and BrCH2CO2Me, respectively, in the pres-
1
ence of KPF6. Spectroscopic data of 13 and 14 including H,
Synthesis of [Ru]-CtCPh (3a). To a Schlenk flask charged
with 2a (0.45 g, 0.69 mmol) was added a solution of NaOMe (2.60
g, 4.81 mmol) in methanol (10 mL). The solution was stirred at
room temperature for 5 min, and the color changed from pink to
yellow. The solvent was removed under vacuum. The desired
product was extracted with 4 × 10 mL of diethyl ether and filtered
31P{1H}, and 13C{1H} NMR spectra clearly reveal the presence
of the vinylidene moiety. Complexes 13 and 14 undergo
deprotonation reaction by Bu4NOH, yielding the cyclopropenyl
complex 15 and the furyl complex 16, respectively; see Scheme
3. The mononuclear system thus displays normal cyclization.
The dinuclear bisvinylidene complex containing bistriethylphos-
phine ligands therefore exhibits distinctive reactivity from that
of the mononuclear system. A multinuclear system could
possibly display even more rich chemistry.
(30) (a) Tadeusz, W.; Maria, B.; Biernat, J. F. J. Organomet. Chem. 1981,
215, 87. (b) Coto, A.; Tenorio, M. J.; Puerta, M. C.; Valerga, P.
Organometallics 1998, 17, 4392. (c) Bruce, M. I.; Wallis, R. C. Aust. J.
Chem. 1979, 32, 1471.

3436 Organometallics, Vol. 26, No. 14, 2007
Liu et al.
Scheme 3
2H, CH2), 2.06-1.76 (m, 24H, CH2), 1.10-0.94 (m, 36H, CH3).
2
13C NMR (CD3COCD3): 344.76 (t, JCP ) 15.5 Hz, CR), 344.44
2
2
(t, JCP ) 15.1 Hz, CR), 343.06 (t, JCP ) 15.1 Hz, CR), 131.38-
128.04 (Ph), 127.44 (Câ), 110.48 (Câ), 90.93 (Cp), 90.83 (Cp), 20.68
(CH2). 31P NMR (CD3COCD3): 38.89, 38.87 (two s, half intensity,
PEt3), 37.50 (s, PEt3). MS FAB m/z: 1091.2 (M+ + 1 - PF6-),
945.3 (M+ + 1 - 2PF6-), 825.2 (M+ + 1 - 2PF6- - PEt3), 709.2
(M+ - +1 - 2PF6- - 2PEt3), 543.3 (M+ - CpRu(PEt3)2), 441.2
(M+ - CpRu(PEt3)2dCdC(Ph)). Anal. Calcd for C45H78F12P6-
Ru2: C, 43.76; H, 6.37. Found: C, 43.80; H, 6.50.
Synthesis of {[Ru]dCdC(Ph)CH2CHdCd[Ru′]}[PF6]2 (5b).
To a Schlenk flask charged with 4a (0.100 g, 0.146 mmol), KPF6
(0.21 g, 1.14 mmol), and 1b (0.106 g, 0.146 mmol) was added
methanol (10 mL) under nitrogen. The solution was stirred at room
temperature for 24 h, and the orange-pink precipitate was filtered
off and washed with methanol (5 mL) twice, then dried under
vacuum to give 5b (0.182 g, 82% yield). 1H NMR (CDCl3): 7.59-
6.86 (m, 35H, Ph); 5.51 (s, 5H, Cp); 4.75 (s, 5H, Cp), 4.54 (t, 3JHH
through Celite. The solvent of the filtrate was removed under
vacuum to give 3a (0.34 g, 98% yield). 1H NMR (CDCl3): 7.66-
7.03 (m, 5H, Ph), 4.74 (s, 5H, Cp), 1.99-1.90 (m, 6H, CH2), 1.37-
1.29 (m, 6H, CH2), 1.07-0.99 (m, 18H, CH3). 13C NMR (CDCl3):
134.68-122.87 (Ph), 118.61 (t, 2JCP ) 25.2 Hz, CR), 110.89 (Câ),
80.78 (Cp). 31P NMR (CDCl3): 40.24 (s, PEt3). MS FAB m/z:
504.1(M+), 403.1 (M+ - CdC(H)Ph). Anal. Calcd for C25H40P2-
Ru: C, 59.62; H, 8.01. Found: C, 59.61; H, 7.92.
3
) 8.1 Hz, 1H, dCH), 3.32 (d, JHH ) 8.1 Hz, 2H, CH2), 1.83-
1.53 (m, 12H, CH2), 0.96-0.85 (m, 18H, CH3). 13C NMR CDCl3:
2
2
350.15 (t, JC-P ) 13.2 Hz, CR), 342.00 (t, JC-P ) 13.1 Hz, CR),
141.45-127.56 (Ph, Câ), 114.15 (Câ), 94.30 (Cp), 92.11 (Cp),
9.00-7.80 (CH2). 31P NMR (CDCl3): 36.15 (s, PEt3), 42.99 (s,
PPh3). MS FAB m/z: 1377.0 (M+ + 1 - PF6-), 1233.1 (M+ + 1
- 2PF6-), 1114.1 (M+ + 1 - 2PF6- - PEt3), 691.1 (M+ - CpRu-
(PEt3)2dCdC(Ph)CH2C(H)dC), 543.1 (M+ - CpRu(PPh3)2). Anal.
Calcd for C69H78F12P6Ru2: C, 54.40; H, 5.16. Found: C, 54.54;
H, 5.48.
Synthesis of {[Ru]dCdC(Ph)CH2CtCH}[PF6] (4a). To a
Schlenk flask charged with 3a (0.10 g, 0.19 mmol) and KPF6
(0.20 g, 1.08 mmol) in CH2Cl2 (10 mL) was added BrCH2CtCH
(0.2 mL, 2.23 mmol) under nitrogen. The clear solution was stirred
for 8 h at room temperature, and the color changed from yellow to
red. Then the solution was filtered through Celite, and the volume
of the filtrate was reduced to 3 mL under vacuum. Diethyl ether
(50 mL) was added to cause precipitation of a pink powder. After
filtration, the precipitate was washed with diethyl ether (5 mL) twice
Synthesis of {[Os]dCdC(Ph)CH2CHdCd[Ru′]}[PF6]2 (5c).
To a Schlenk flask charged with 4c (0.10 g, 0.09 mmol), KPF6
(0.02 g, 0.10 mmol), and 1b (0.07 g, 0.10 mmol) was added
methanol (15 mL) under nitrogen. The solution was heated to reflux
for 4 h. After cooling, the solvent was removed in vacuo, and CH2-
Cl2 (2 × 5 mL) was used to extract the product. The resulting
solution was filtered through Celite, concentrated to ca. 5 mL, and
added to diethyl ether (60 mL) to produce a purple precipitate,
which was filtered, washed with diethyl ether, and dried under
1
and dried under vacuum to give 4a (0.12 g, 92% yield). H NMR
4
(CDCl3): 7.37-7.20 (m, 5H, Ph); 5.56 (s, 5H, Cp); 3.32 (d, JHH
4
) 2.6 Hz, 2H, CH2), 2.13 (t, JHH ) 2.6 Hz, 1H, tCH), 1.93-
1
1.58 (m, 12H, CH2), 1.04-0.92 (m, 18H, CH3). 13C NMR
vacuum to give 5c (0.14 g, 80% yield). H NMR (CD3COCD3):
2
7.79-7.04 (m, 65H, Ph), 5.67 (s, 5H, CpOs), 4.91 (s, 5H, CpRu),
(CDCl3): 345.93 (t, JCP ) 14.7 Hz, CR), 133.49-127.61 (Ph),
3
3
4.70 (t, JHH ) 5.96 Hz, 1H, CH), 3.24 (d, JHH ) 5.96 Hz, 2H,
123.68 (Câ), 90.50 (Cp), 82.22 (HCtC), 70.53 (HCtC), 17.10
(CH2). 31P NMR (CDCl3): 36.96 (s, PEt3). MS FAB m/z: 543.3
(M+ - PF6), 514.2 (M+ - C2H5). Anal. Calcd for C28H43F6P3Ru:
C, 48.91; H, 6.30. Found: C, 49.05; H, 6.22.
CH2). 13C{1H} NMR CD3COCD3: 345.96 (t, JCP ) 14.5 Hz,
RuCR), 304.62 (t, JCP ) 9.7 Hz, OsCR), 135.22-128.52 (m, Ph
2
2
and RuCâ), 114.7 (OsCâ), 94.6 (CpRu), 92.3 (CpOs), 15.7 (CH2).
31P{1H} NMR (CD3COCD3): 42.16 (s, RuPPh3); -4.86 (s, Os-
PPh3). MS FAB m/z: 1756.2 (M+ + 1 - PF6-), 1611.2 (M+ + 1
- 2PF6), 1347.1 (M+ + 1 - 2PF6 - PPh3), 1085 (M+ + 1 - 2PF6
- 2PPh3). Anal. Calcd for C93H78F12P6RuOs: C, 58.76; H, 4.14.
Found: C, 59.02; H, 4.45.
Synthesis of {[Os]dCdC(Ph)CH2CtCH}[PF6] (4c). To a
Schlenk flask charged with [Os]CtCPh (0.50 g, 0.57 mmol) and
KPF6 (0.11 g, 0.6 mmol) were added CH2Cl2 (20 mL) and
BrCH2CtCH (0.4 mL, 4.46 mmol) under nitrogen. The resulting
solution was stirred for 8 h at room temperature. Then the solvent
was removed in vacuo, and CH2Cl2 (2 × 5 mL) was used to extract
the product. After filtration, the volume of the filtrate was reduced
to ca. 5 mL. Then the filtrate was added to diethyl ether (60 mL)
to yield a pale red precipitate, which was filtered, washed with
diethyl ether, and recrystallized from CH2Cl2/hexane to give 4c
Synthesis of {[Ru]dCdC(Ph)CH2CtC-[Ru]}PF6 (6a). To
a Schlenk flask charged with 5a (0.10 g, 0.081 mmol) and NaOMe
(0.05 g, 0.93 mmol) was added methanol (5 mL). The solution was
stirred at room temperature for 30 min, and the color changed from
pink to deep yellow. The solvent was removed under vacuum and
CH2Cl2 (2 × 5 mL) was used to extract the product. The solution
was filtered through a sintered glass with Celite, then the volume
of the filtrate was reduced to 3 mL and diethyl ether (50 mL) was
added to cause precipitation of an orange powder. After filtration,
the precipitate was washed with diethyl ether (2 × 5 mL) and dried
1
(0.60 g, 90%). H NMR (CD3COCD3): 7.48-7.06 (m, 35H, Ph),
4
4
5.70 (s, 5H, Cp), 3.24 (d, JHH ) 2.6 Hz, 2H, CH2), 2.66 (t, JHH
) 2.6 Hz, 1H, CH). 31P{1H} NMR (δ, d6-acetone): -5.33 (s, PPh3).
MS FAB m/z: 1011.2 (M+ - PF6). Anal. Calcd for C52H43F6P3-
Os: C, 58.64; H, 4.07. Found: C, 58.72; H, 4.35.
1
under vacuum to give 6a (82 mg, 93% yield). H NMR (CD3-
Synthesis of {[Ru]dCdC(Ph)CH2CHdCd[Ru]}[PF6]2 (5a).
To a Schlenk flask charged with 4a (50 mg, 0.073 mmol), KPF6
(0.11 g, 0.60 mmol), and 1a (32 mg, 0.073 mmol) was added
methanol (7 mL) under nitrogen. The solution was stirred at room
temperature for 19 h, and the pink precipitate was filtered off and
washed with methanol (2 mL) twice and ether (10 mL), then dried
COCD3): 7.48-7.18 (m, 5H, Ph), 5.79 (s, 5H, Cp), 4.61 (s, 5H,
Cp), 3.63 (s, 2H, CH2), 1.96-1.88 (m, 12H, CH2), 1.50-1.30 (m,
12H, CH2), 1.11-0.95 (m, 36H, CH3). 13C NMR (CD3COCD3):
350.45 (t, 2JCP ) 14.8 Hz, CR), 132.57-126.87 (Ph), 119.17 (Câ),
2
110.29 (t, JCP ) 11.8 Hz, CR), 101.30 (Câ), 87.54 (Cp), 85.85
1
under vacuum to give 5a (72 mg, 80% yield). H NMR (CD3-
(Cp), 15.20 (CH2). 31P NMR (CD3COCD3): 38.88 (s, PEt3), 36.03
(s, PEt3). MS FAB m/z: 1091.3 (M+ + 1), 945.3 (M+ + 1 - PF6),
826.2 (M+ + 1 - PF6 - PEt3), 709.2 (M+ + 1 - PF6 - 2PEt3),
COCD3): 7.53-7.37 (m, 5H, Ph), 5.79 (s, 5H, Cp), 5.34, (s, 5H,
3
3
Cp), 4.46 (t, JHH ) 8.1 Hz, 1H, dCH), 3.72 (d, JHH ) 8.1 Hz,

Preparation of Dinuclear Vinylidene Complexes
Organometallics, Vol. 26, No. 14, 2007 3437
Table 3. Crystal Data and Structure Refinement Parameters for Complexes 6b and 9a
6b
9a
empirical formula
fw
C70H79Cl2F6P5Ru2
1462.22
C47H78F6NP5Ru2
1128.09
temperature [K]
cryst syst
space group
a [Å]
b [Å]
c [Å]
295(2)
monoclinic
P21/n
15.3762(2)
13.8246(2)
32.2115(5)
95.0360(4)
6820.76(17), 4
1.424
0.695
3000
0.25 × 0.20 × 0.15
1.27-25.00
37 452
295(2)
monoclinic
P21/c
9.2924(2)
21.0916(4)
27.4615(4)
90.1850(10)
5382.19(17), 4
1.392
0.762
2336
0.15 × 0.15 × 0.10
2.19-25.00
29 613
â [deg]
volume [Å3], Z
F
cacld [Mg m-3
]
absorp coeff [mm-1
F(000)
]
cryst size [mm3]
2θ [deg]
no. of reflns collected
no. of indep reflns
11 803
9259
R(int)
0.0391
0.0549
no. data/restraints/params
goodness-of-fit on F2
final R indices [I >2σ(I)]
R indices (all data)
11803/0/742
1.100
R1 ) 0.0597, wR2 ) 0.1679
R1 ) 0.0734, wR2 ) 0.1879
0.998/-0.668
9259/0/544
1.089
R1 ) 0.0612, wR2 ) 0.1544
R1 ) 0.0980, wR2 ) 0.1774
0.674/-0.583
largest diff peak/hole [e Å-3
]
543.3 (M+ - CpRu(PEt3)2). Anal. Calcd for C45H77F6P5Ru2: C,
to a solution of diethyl ether (50 mL), giving a pink precipitate.
After filtration, the precipitate was washed with diethyl ether and
dried under vacuum to give 7a (0.050 g, 84% yield). 1H NMR (CD3-
COCD3): 7.59-7.54 (m, 5H, Ph), 5.91 (s, 5H, Cp), 5.39 (s, 5H,
Cp), 3.83 (s, 2H, CH2), 3.03 (s, 2H, CH2), 2.02-1.91 (m, 24H,
CH2), 1.18-0.97 (m, 36H, CH3). 13C NMR (CD3COCD3): 339.45
(t, JCP ) 14.6 Hz, CR), 338.97 (t, JCP ) 14.6 Hz, CR), 131.88-
128.21 (Ph), 124.04 (Câ), 119.77 (Câ), 114.20 (CtN), 25.18 (CH2-
CN), 14.80 (CH2). 31P NMR (CD3COCD3): 36.39 (s, PEt3), 35.47
(s, PEt3). MS FAB m/z: 1129.3 (M+ - PF6-), 866.2 (M+ - PEt3),
746.2 (M+ - 2PEt3), 610.3 (M+ - 3PEt3), 504.2 (M+ - CpRu-
(PEt3)2dCdC(CH2CN)CH2). Anal. Calcd for C47H79F12NP6Ru2: C,
44.31; H, 6.25; N, 1.10. Found: C, 44.54; H, 6.48; N, 1.25.
49.63; H, 7.13. Found: C, 49.51; H, 7.10.
Synthesis of {[Ru]dCdC(Ph)CH2CtC-[Ru′]}PF6 (6b). To
a Schlenk flask charged with 5b (0.10 g, 0.066 mmol) and NaOMe
(0.05 g, 0.93 mmol) was added methanol (5 mL). The solution was
stirred at room temperature under nitrogen for 30 min, yielding a
yellow precipitate, which was filtered and washed with diethyl ether
and dried under vacuum to give 6b (0.079 g, 87% yield). Single
crystals were grown by slow diffusion of diethyl ether into a
2
2
1
saturated CH2Cl2 solution of 6b. H NMR (CD3COCD3): 7.56-
7.09 (m, Ph); 5.75 (s, 5H, Cp); 4.18 (s, 5H, Cp), 3.73 (s, 2H, CH2),
2.14-1.95 (m, 12H, CH2), 1.15-1.03 (m, 18H, CH3). 13C NMR
2
(CD3COCD3): 350.23 (t, JC-P ) 15.5 Hz, CR), 134.61-127.01
(Ph, Câ), 107.05 (Câ), 97.80 (t, 2JC-P ) 24.0 Hz, CR), 90.95 (Cp),
Synthesis of 7b. To a Schlenk flask charged with 6b (0.05 g,
0.036 mmol), KPF6 (0.10 g, 0.54 mmol), and CH2Cl2 (5 mL) under
nitrogen was added ICH2CN (0.060 mL, 0.827 mmol) at room
temperature. The color of the solution changed from yellow to red
in 15 min. Then the solution was filtered through Celite, and the
volume of the filtrate was reduced to 3 mL under vacuum. The
mixture was slowly added to of a solution of diethyl ether (50 mL),
giving a precipitate. After filtration, the precipitate was washed with
diethyl ether and dried under vacuum to give 7b (0.046 g, 80%
85.75 (Cp), 10.08 (CH2). 31P NMR (CD3COCD3): 48.99 (s, PPh3),
36.15 (s, PEt3). MS FAB m/z: 1232.1 (M+ - PF6), 1114.1 (M+
-
PF6 - PEt3), 970.1 (M+ - PF6 - PPh3), 850.9 (M+ - PF6 - PPh3
- PEt3), 729.0 (M+ - PF6 - CpRu(PEt3)2dCdC(Ph)), 543.1 (M+
- CpRu(PPh3)2), 467.0 (M+ - CpRu(PPh3)2 - Ph). Anal. Calcd
for C69H77F6P5Ru2: C, 60.17; H, 5.63. Found: C, 60.05; H, 5.53.
{[Os]dCdC(Ph)CH2CtC-[Ru′]}[PF6] (6c). To a Schlenk
flask charged with 5c (0.10 g, 0.05 mmol) and NaOMe (0.01 g,
0.20 mmol) was added acetone (10 mL). The resulting solution
was stirred at room temperature for 30 min, and the color changed
from purple to deep yellow. The solvent was removed in vacuo,
and CH2Cl2 (2 × 5 mL) was used to extract the product. The
resulting solution was filtered through Celite, concentrated to ca.
5 mL, and added to diethyl ether (60 mL) to produce a brown
precipitate, which was filtered, washed with diethyl ether, and dried
1
yield). H NMR (CD3COCD3): 7.78-7.04 (m, Ph); 5.91 (s, 5H,
Cp), 5.09 (s, 5H, Cp), 3.64 (s, 2H, CH2), 3.47 (s, 2H, CH2), 2.00-
1.91 (m, 12H, CH2), 1.07-0.95 (m, 18H, CH3). 13C NMR (CD3-
2
2
COCD3): 342.91 (t, JCP ) 15.2 Hz, CR), 337.96 (t, JCP ) 14.3
Hz, CR), 135.37-129.08 (Ph), 123.44 (Câ), 119.73 (Câ), 117.42
(CtN), 95.99 (Cp), 91.93 (Cp), 26.05 (CH2CN), 13.50 (CH2). 31
P
NMR (CD3COCD3): 39.46 (s, PPh3), 35.54 (s, PEt3). MS FAB
m/z: 1272.4 (M+), 1010.5 (M+ - PPh3), 892.5 (M+ - PPh3 -
PEt3), 504.4 (M+ - CpRu(PPh3)2dCdC(CH2CN)CH2). Anal. Calcd
for C71H79NF12P6Ru2: C, 54.58; H, 5.10; N, 0.90. Found: C, 54.91;
H, 5.04; N, 1.02.
1
under vacuum to give 6c (0.08 g, 88% yield). H NMR (CD3-
COCD3): 7.46-7.04 (m, 65H, Ph), 5.62 (s, 5H, CpOs), 4.26 (s,
5H, CpRu), 3.68 (s, 2H, CH2). 13C NMR (CD3COCD3): 301.82 (t,
2
2JCP ) 10.0 Hz, OsCR), 139.14 (t, JCP ) 21.2 Hz, RuCR), 117.97
(OsCâ), 107.21 (s, RuCâ), 91.59 (CpRu), 84.74 (CpOs), 17.27(CH2).
31P{1H} NMR (CD3COCD3): 48.76 (s, RuPPh3), -4.05 (s, Os-
PPh3). Anal. Calcd for C93H77F6P5RuOs: C, 63.65; H, 4.42.
Found: C, 63.70; H, 4.61.
Synthesis of {[Os]dCdC(Ph)CH2C(CH2CN)dCd[Ru′]}-
[PF6]2 (7c). To a Schlenk flask charged with 6c (0.090 g, 0.050
mmol), CH2Cl2 (10 mL), and KPF6 (0.010 g, 0.06 mmol) was added
ICH2CN (0.02 mL, 0.276 mmol). The resulting solution was heated
to reflux for 8 h. The solvent was removed under vacuum, and
CH2Cl2 was used to extract the product. Then the solution was
filtered through Celite, and the filtrate was concentrated to ca.
5 mL and added to a solution of diethyl ether (60 mL) to produce
a purple precipitate. The powder was filtered, washed with diethyl
ether, and recrystallized from CH2Cl2/hexane to give 7c (0.080 g,
78% yield). 1H NMR (CD3COCD3): 7.75-6.89 (m, 65H, Ph), 5.86
Synthesis of 7a. To a Schlenk flask charged with 6a (0.05 g,
0.046 mmol) and KPF6 (0.11 g, 0.60 mmol) was added CH2Cl2
(5 mL) under nitrogen. The resulting solution was stirred at room
temperature, and ICH2CN (0.05 mL, 0.689 mmol) was added. After
stirring for 15 min, the color changed from yellow to red. Then
the solution was filtered through Celite, and volume of the filtrate
was reduced to 3 mL under vacuum. The mixture was slowly added

3438 Organometallics, Vol. 26, No. 14, 2007
Liu et al.
(s, 5H, CpRu), 4.87 (s, 5H, CpOs), 3.66 (br s, 2H, CH2), 3.00 (s,
then CH2Cl2 (5 mL) was added and the solution was filtered through
Celite. The volume of the filtrate was reduced to 3 mL under
vacuum. A solution of diethyl ether (50 mL) was added to cause
precipitation of a purple-red powder. After filtration, the precipitate
was washed with diethyl ether and dried under vacuum to give 9b.
Single crystals were obtained by slow diffusion of diethyl ether
2
2H, CH2). 13C NMR (CD3COCD3): 341.51 (t, JCP ) 15.1 Hz,
2
RuCR), 302.24 (t, JCP ) 8.7 Hz, OsCR), 135.43-126.96 (m, Ph),
123.7 (RuCâ), 120.3 (OsCâ), 118.3 (CN), 95.9 (CpRu), 93.5 (CpOs),
22.8 (CH2CN), 14.1 (CH2). 31P{1H} NMR (CD3COCD3): 39.51
(br s, RuPPh3); -6.33 (br s, OsPPh3). Anal. Calcd for C95H79F12-
NP6RuOs: C, 58.82; H, 4.11; N, 0.72. Found: C, 59.02; H, 4.25;
N, 0.81.
1
into a saturated CH2Cl2 solution of 9b. H NMR (CD3COCD3):
7.42-7.14 (m, Ph); 5.38 (s, 5H, Cp), 5.05 (s, 1H, CH), 4.82 (s,
5H, Cp), 4.54, 4.09 (two d, 2JHH ) 18.1 Hz, 2H, CH2), 1.75-0.80
Synthesis of {[Ru]dCdC(Ph)CH2C(CH2COOEt)dCd[Ru]}-
[PF6]2 (8a). To a Schlenk flask charged with 6a (0.10 g, 0.092
mmol) and KPF6 (0.10 g, 0.54 mmol) was added CH2Cl2 (5 mL).
The resulting solution was stirred at room temperature, and ethyl
iodoacetate (0.13 mL, 1.09 mmol) was added. After 14 h, the color
changed from yellow to red. Then the solution was filtered through
Celite, and volume of the filtrate was reduced to 3 mL under
vacuum. The mixture was slowly added to a solution of diethyl
ether (50 mL). After filtration, the precipitate was washed with
diethyl ether and dried under vacuum to give 8a (0.091 g, 75%
2
(m, 30H, PEt3). 13C NMR (CD3COCD3): 341.46 (t, JCP ) 11.8
2
Hz, CR), 149.07 (t, JCP ) 11.6 Hz, CR), 143.22 (Câ), 129.33-
127.00 (Ph, CtN), 125.60 (CPh), 95.09 (Cp), 79.89 (Cp), 54.91
(CCtN), 47.08 (CH2). 31P NMR (CD3COCD3): 39.73, 37.88 (two
2
2
d, JPP ) 32.6 Hz, PPh3), 29.77, 29.36 (two d, JPP ) 45.9 Hz,
PEt3). MS FAB m/z: 1271.2 (M+ - PF6), 1154.1 (M+ - PF6 -
PEt3), 892.1 (M+ - PF6 - PEt3 - PPh3), 774.1 (M+ - PF6 -
2PEt3 - PPh3), 403.1 (M+ - CpRu(PPh3)2dCdC(CHCN)CH2C-
(Ph)dC). Anal. Calcd for C71H78F6NP5Ru2: C, 60.21; H, 5.55; N,
0.99. Found: C, 60.42; H, 5.12; N, 1.09.
1
yield). H NMR (CD3COCD3): 7.56-7.37 (m, 5H, Ph), 5.86 (s,
3
5H, Cp), 5.31 (s, 5H, Cp), 4.25 (q, JHH ) 6.9 Hz, 2H, OCH2),
Synthesis of 10b. To a 5 mL acetone solution of 7b (0.050 g,
0.032 mmol) at room temperature under nitrogen was added n-Bu4-
NOH (0.20 mL, 0.20 mmol). After 10 min, the solvent was removed
under vacuum and diethyl ether was used to extract the product.
Then the solution was filtered through a sintered glass with Celite,
and the solvent was removed under vacuum to give 10b. 1H NMR
(CD3COCD3): 7.08-6.97 (m, 35H, Ph); 4.76 (s, 5H, Cp), 4.16 (s,
3.75 (s, 2H, CH2), 3.43 (s, 2H, CH2), 2.00-1.75 (m, 24H, CH2),
3
1.32 (t, JHH ) 6.9 Hz, 3H, CH3), 1.21-0.85 (m, 36H, CH3). 31P
NMR (CD3COCD3): 36.47 (s, PEt3), 35.58 (s, PEt3). Anal. Calcd
for C49H84F12O2P6Ru2: C, 44.55; H, 6.41. Found: C, 44.76; H,
6.58.
Synthesis of {[Ru]dCdC(Ph)CH2C(CH2COOEt)dCd[Ru′]}-
[PF6]2 (8b). To a Schlenk flask charged with 6b (0.10 g, 0.073
mmol) and KPF6 (0.10 g, 0.54 mmol) in CH2Cl2 (5 mL) was added
ethyl iodoacetate (0.14 mL, 1.18 mmol) at room temperature. After
20 h, the color changed from yellow to red. Then the solution was
filtered through Celite, and volume of the filtrate was reduced to 3
mL under vacuum. The mixture was slowly added to a solution of
diethyl ether (50 mL), giving a pink precipitate, which, after
filtration, was washed with diethyl ether and dried under vacuum
2
5H, Cp), 3.53, 3.46 (two d, JHH ) 16.5 Hz, 2H, CH2). 13C NMR
(CD3COCD3): 140.37 (t, 2JCP ) 5.9 Hz, CR), 134.93-124.93 (Ph,
Câ), 108.53 (Câ), 93.74 (CtN), 85.68 (Cp), 85.66 (Cp). 31P NMR
2
(CD3COCD3): 51.07, 50.68 (two d, JPP ) 39.8 Hz, PPh3), 35.78
(s, PEt3). MS FAB m/z: 1271.4 (M+ - PF6), 1011.2 (M+ - PF6
- PPh3), 892.2 (M+ - PF6 - PEt3 - PPh3), 691.2 (M+ - CpRu-
(PEt3)2dCdC(Ph)CH2C(CHCN)dC), 403.2 (M+ - CpRu(PPh3)2d
CdC(CHCN)CH2C(Ph)dC). Anal. Calcd for C71H78F6NP5Ru2: C,
60.21; H, 5.55; N, 0.99. Found: C, 60.72; H, 5.65; N, 1.11.
1
to give 8b (0.102 g, 87% yield). H NMR (CD3COCD3): 7.70-
7.09 (m, 35H, Ph), 5.86 (s, 5H, Cp), 4.99 (s, 5H, Cp), 4.19 (q,
3JHH ) 7.2 Hz, 2H, OCH2), 3.77 (s, 2H, CH2), 3.37 (s, 2H, CH2),
1.95-1.87 (m, 12H, CH2), 1.24 (t, 3JHH ) 7.2 Hz, 3H, CH3), 1.14-
0.94 (m, 18H, CH3). 31P NMR (CD3COCD3): 40.40 (s, PPh3), 35.99
(s, PEt3). Anal. Calcd for C73H84F12O2P6Ru2: C, 54.48; H, 5.26.
Found: C, 54.59; H, 5.08.
Deprotonation of 7c. To a solution of 7c (0.10 g, 0.05 mmol)
in 15 mL of acetone was added a solution of n-Bu4NOH (0.2 mL,
1 M in MeOH). The mixture was stirred for 30 min to yield the
light yellow microcrystalline powder, which was filtered, washed
with 2 × 3 mL of acetone and 2 × 5 mL of diethyl ether, and
1
dried under vacuum to give 10c (0.075 g, 80% yield). H NMR
(CD3COCD3): 7.42-6.96 (m, 65H, Ph), 5.75 (s, 5H, CpOs), 4.54
Synthesis of 9a. A mixture of 7a (0.050 g, 0.039 mmol) and
NaOMe (0.030 g, 0.556 mmol) was dissolved in 10 mL of acetone
at room temperature. The solution was stirred under nitrogen for
20 min, and the color changed from pink to deep yellow. After
removal of the solvent in vacuo, CH2Cl2 was added to the residue,
and the extract was filtered with Celite. The volume of the filtrate
was reduced to about 3 mL, and hexane (50 mL) was added to
cause precipitation of deep brown solid, which was collected by
filtration and washed with diethyl ether and hexane, affording 9a
(0.035 g, 80% yield). 1H NMR (CD3COCD3): 7.40-7.20 (m 5H,
Ph), 5.71 (s, 5H, Cp), 5.08 (s, 1H, CH), 4.82 (s, 5H, Cp), 4.42,
4.21 (two d, 2JHH ) 17.4 Hz, 2H, CH2), 1.97-0.74 (m, 60H, PEt3).
(b, 1H, CH), 4.48 (s, 5H, CpRu), 3.02 (br, 1H, CH2), 3.00 (br, 1H,
2
CH2). 13C{1H} NMR (CD3COCD3): 307.23 (t, JCP ) 9.3 Hz,
2
OsCR), 139.86 (t, JCP ) 5.8 Hz, RuCR), 135.41-126.94 (m, Ph
and RuCâ), 124.8 (OsCâ), 95.9 (CN), 93.2 (CpOs), 86.2 (CpRu),
20.3 (CH); 15.5 (CH2). 31P{1H} NMR (CD3COCD3): 50.4, 48.4
(two d, Jpp ) 35.2 Hz, RuPPh3), -3.9, -5.8 (two d, Jpp) 19.5 Hz,
OsPPh3). Anal. Calcd for C95H78F6NP5RuOs: C, 63.61; H, 4.38;
N, 0.78. Found: C, 63.72; H, 4.71; N, 0.93.
Deprotonation of 8a. A mixture of 8a (0.050 g, 0.038 mmol)
and sodium methoxide (0.02 g, 0.37 mmol) was dissolved in
10 mL of acetone at room temperature. After 70 min, the solvent
was removed in vacuo, CH2Cl2 was added to the residue, and the
extract was filtered through Celite. The volume of the filtrate was
reduced to about 3 mL, and 50 mL of hexane was added to cause
precipitation of a pink-purple powder. The solid was collected by
filtration followed by washing with diethyl ether and hexane. The
solid was dried under vacuum to afford the product 11a and other
unidentified side products (0.04 g) in an 8:1 ratio based on NMR
data. Attempts to further purify the desired product caused extensive
decomposition of 11a. Spectroscopic data were used to identify
11a. 1H NMR (CD3COCD3): 7.51-7.19 (m, 5H, Ph), 5.57 (s, 5H,
Cp), 4.94 (s, 1H, CH), 4.62 (s, 5H, Cp), 4.24 (m, 2H, CH2), 4.17,
4.05 (m, 2H, OCH2), 1.30 (m, 3H, CH3), 2.13-0.70 (m, 60H, PEt3).
2
13C NMR (CD3COCD3): 339.81 (t, JCP ) 15.0 Hz, CR), 149.34
(t, 2JCP ) 14.2 Hz, CR), 144.31 (Câ), 131.55-126.26 (Ph), 124.82
(CN), 121.38 (CPh), 90.86 (Cp), 79.84 (Cp), 56.04 (CH), 46.26
2
(CH2). 31P NMR (CD3COCD3): 39.73, 37.88 (two d, JPP ) 32.6
2
Hz, PEt3), 29.77, 29.36 (two d, JPP ) 45.9 Hz, PEt3). MS FAB
m/z: 1129.3 (M+ + 1), 984.4 (M+ + 1 - PF6), 866.3 (M+ + 1 -
PF6 - PEt3), 747.2 (M+ + 1 - PF6 - 2PEt3), 628.1 (M+ + 1 -
PF6 - 3PEt3), 582.3 (M+ - 3PEt3 - 3CH3), 403.2 (M+ - CpRu-
(PEt3)2dCdC(CH2CN)CH2C(Ph)dC). Anal. Calcd for C47H78F6-
NP5Ru2: C, 50.04; H, 6.97; N, 1.24. Found: C, 50.25; H, 6.78; N,
1.48.
Synthesis of 9b. To a Schlenk flask charged with 7b (0.050 g,
0.032 mmol) and NaOMe (0.03 g, 0.39 mmol) was added acetone
(5 mL). After 30 min, the solvent was removed under vacuum,
2
13C NMR (CD3COCD3): 339.39 (t, JCP ) 15.3 Hz, CR), 175.94
(CO), 152.80 (t, 2JCP ) 14.1 Hz, CR), 144.33 (Câ), 132.03-126.45

Preparation of Dinuclear Vinylidene Complexes
Organometallics, Vol. 26, No. 14, 2007 3439
2
(Ph), 123.56 (CPh), 90.04 (Cp), 78.79 (Cp), 69.46 (CH), 60.63
13C NMR (CD3COCD3): 346.87 (t, JCP ) 14.6 Hz, CR), 172.83
(OCH2), 47.60 (CH2), 14.50 (CH3). 31P NMR (CD3COCD3): 39.68,
(CO), 134.55-128.08 (Ph), 123.60 (Câ), 91.75 (Cp), 52.40 (OCH3),
2
2
37.42 (two d, JPP ) 32.7 Hz, PEt3), 31.09, 28.92 (two d, JPP
)
32.95 (CH2). 31P NMR (CD3COCD3): 35.58 (s, PEt3). MS FAB
47.9 Hz, PEt3).
m/z: 577.2 (M+), 458.1 (M+ - PEt3), 401.0 (M+ - PEt3
-
Deprotonation of 8b. Complex 8b (50 mg, 0.031 mmol) in
0.5 mL of d6-acetone was treated with n-Bu4NOH (50 µL, 1 M
MeOH solution) at room temperature. The color of the solution
turned yellow immediately. The 31P NMR spectrum of the crude
product indicated clean formation of the furyl complex 12b.
Attempts to isolate the product resulted in complete decomposition
of the desired product. Complex 12b was characterized only by
31P NMR. Spectroscopic data for 12b: 31P NMR (CD3COCD3):
49.45 (s, PPh3), 36.49 (s, PEt3).
Synthesis of {[Ru]dCdC(Ph)CH2CN}[PF6] (13). To a Schlenk
flask charged with 3a (0.100 g, 0.20 mmol) and KPF6 (0.21 g, 1.08
mmol) in CH2Cl2 (10 mL) was added ICH2CN (0.1 mL, 1.38
mmol). After 30 min at room temperature, the solution was filtered
through Celite, and the volume of the filtrate was reduced to 3 mL
under vacuum. An aliquot of diethyl ether (50 mL) was added to
cause precipitation of a pink powder, which, after filtration, was
washed with diethyl ether and dried under vacuum to give 13
(0.126 g, 92% yield). 1H NMR (CD3COCD3): 7.45-7.30 (m, 5H,
Ph); 5.95 (s, 5H, Cp); 3.87 (s, 2H, CH2), 2.12-1.94 (m, 12H, CH2),
1.12-1.01 (m, 18H, CH3). 13C NMR (CD3COCD3): 341.54 (t, 2JCP
) 14.6 Hz, CR), 133.30-128.00 (Ph), 120.05 (Câ), 118.59 (CN),
91.10 (Cp), 16.49 (CH2). 31P NMR (CD3COCD3): 35.51 (s, PEt3).
MS FAB m/z: 544.2 (M+), 427.1 (M+ - PEt3). Anal. Calcd for
C27H42F6NP3Ru: C, 47.09; H, 6.15; N, 2.03. Found: C, 47.24; H,
6.41; N, 2.25.
COOMe), 341.0 (M+ - 2PEt3). Anal. Calcd for C28H45F6O2P3Ru:
C, 46.60; H, 6.29. Found: C, 46.59; H, 6.24.
Synthesis of Furyl Complex 16. To a 5 mL acetone solution of
14 (0.05 g, 0.08 mmol) at room temperature was added n-Bu4NOH
(0.5 mL, 0.43 mmol). After 5 min the solvent was removed under
vacuum and diethyl ether (5 mL) was added to extract the product.
The solution was filtered, and the filtrate was dried under vacuum
1
to give 16 (0.04 g, 90% yield). H NMR (C6D6): 7.78-7.30 (m,
5H, Ph); 5.26 (s, 1H, CH), 4.47 (s, 5H, Cp); 3.52 (s, 3H, OMe),
1.86-0.80 (m, 30H, PEt3). 31P NMR (C6D6): 40.22 (s, PEt3). MS
FAB m/z: 577.2 (M+ + 1), 459.2 (M+ - PEt3), 403.2 (M+
-
CdC(Ph)CH2COOMe). Anal. Calcd for C28H44O2P2Ru: C, 58.42;
H, 7.70. Found: C, 58.30; H, 7.94.
Single-Crystal X-ray Diffraction Analysis of 6b and 9a. Single
crystals of 6b suitable for an X-ray diffraction study were grown
as mentioned above. A single crystal of dimensions 0.25 × 0.20 ×
0.15 mm3 was glued to a glass fiber and mounted on a SMART
CCD diffractometer. The diffraction data were collected using 3
kW sealed-tube Mo KR radiation (T ) 295 K). Exposure time was
5 s per frame. SADABS31 (Siemens area detector absorption)
absorption corrections were applied, and decay was negligible. Data
were processed, and the structure was solved and refined by the
SHELXTL32 program. The structure was solved using direct
methods and confirmed by Patterson methods refining on intensities
of all data to give R1 ) 0.0597 and wR2 ) 0.1679 for 11 803
unique observed reflections (I > 2σ(I)). Hydrogen atoms were
placed geometrically using the riding model with thermal parameters
set to 1.2 times that for the atoms to which the hydrogen is attached
and 1.5 times that for the methyl hydrogens. An X-ray diffraction
study of 9a was carried out on a single crystal of dimensions 0.15
× 0.15 × 0.10 mm3. The structure was similarly solved to give R1
) 0.0612 and wR2 ) 0.1554 for 9259 unique observed reflections
(I > 2σ(I)). Appropriate crystal data and structure refinement
parameters for complexes 6b and 9a are listed in Table 3.
Deprotonation of 13. To a 5 mL acetone solution of 13
(0.050 g, 0.073 mmol) at room temperature was added n-Bu4NOH
(0.5 mL, 0.42 mmol). After 1 min the solvent was removed under
vacuum and diethyl ether (5 mL) was added to extract the product.
Then the solution was filtered through a sintered glass with Celite
and the solvent was removed under vacuum to give 15 (0.034 g,
87% yield). 1H NMR (C6D6): 7.90-7.30 (m, 5H, Ph); 4.94 (s, 5H,
Cp); 1.50 (s, 1H, CH), 1.62-0.60 (m, 30H, PEt3). 31P NMR
2
(C6D6): 42.16, 41.67 (dd, JPP ) 38.0 Hz, PEt3). MS FAB m/z:
544.2 (M+ + 1). Anal. Calcd for C41H27NP2Ru: C, 59.76; H, 7.62;
N, 2.58. Found: C, 59.90; H, 7.44; N, 2.62.
Acknowledgment. This research is supported by the Na-
Synthesis of {[Ru]dCdC(Ph)CH2COOMe}[PF6] (14). To a
Schlenk flask charged with 3a (0.12 g, 0.239 mmol) and KPF6
(0.20 g, 1.08 mmol) in CH2Cl2 (10 mL) was added methylbro-
moacetate (0.7 mL, 7.37 mmol). After 15 h at room temperature,
the solution was filtered through Celite, and the volume of the
filtrate was reduced to 3 mL under vacuum. An aliquot of diethyl
ether (50 mL) was added to cause precipitation of a pink powder,
which, after filtration, was washed with diethyl ether and dried under
tional Science Council of Taiwan, Republic of China.
Supporting Information Available: Complete crystallographic
data for 6b and 9a (CIF). This material is available free of charge
via the Internet at http://pubs.acs.org.
OM060641O
(31) The SADABS program is based on the method of Blessing; see:
Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(32) SHELXTL, Structure Analysis Program, version 5.04; Siemens
Industrial Automation Inc.: Madison, WI, 1995.
1
vacuum to give 14 (0.11 g, 95% yield). H NMR (CD3COCD3):
7.70-7.15 (m, 5H, Ph); 5.88 (s, 5H, Cp); 3.65 (s, 3H, OCH3), 3.57
(s, 2H, CH2), 2.89-2.01 (m, 12H, CH2), 1.10-0.99 (m, 18H, CH3).