σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands

Article abstract of DOI:10.1016/S0022-328X(03)00003-2

The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans -[(dppm)₂ClMC≡CSi(Ph)₂C≡CH] (M = Ru 1; O

Full text of DOI:10.1016/S0022-328X(03)00003-2

Journal of Organometallic Chemistry 671 (2003) 27Á34
/
www.elsevier.com/locate/jorganchem
s-Acetylide complexes of ruthenium and osmium containing
alkynylsilane ligands
Wai-Yeung Wong *, Chun-Kin Wong, Guo-Liang Lu
Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong
Received 25 November 2002; received in revised form 2 January 2003; accepted 2 January 2003
Abstract
The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal s-
acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm) CSi(Ph) CꢀCH] (MꢀRu 1; Os 2) and
ClMCꢀ
Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture
CH or HCꢀCSi(Me) OÁSi(Me) CꢀCH in the presence of NaPF followed by
2
/
2
/
/
trans-[(dppm) ClMCꢀ
/
CSi(Me)2Á
/
OÁ
/
Si(Me) Cꢀ
/
CH] (Mꢀ
/
2
2
of cis-[M(dppm)
2
Cl
2
] and HCꢀ
/
CSi(Ph)
2
Cꢀ
/
/
2
Á
/
/
2
/
6
deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR
spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two
diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1Á
show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting
precursors cis-[M(dppm) Cl ] (MꢀRu, Os).
2003 Elsevier Science B.V. All rights reserved.
/
4
2
2
/
#
Keywords: Alkynyl complexes; Ruthenium; Osmium; Silane; Siloxane
1
. Introduction
gain insight in this area has been to investigate the
factors that contribute to the extent of p-electron
delocalization in the main chain by varying the metal
centre, the auxiliary ligands and the connecting organic
functionalities [2]. While much research effort has been
devoted to the use of aromatic [3], heteroaromatic [4] or
oligoacetylenic spacers [5], very few reports were known
for the silicon-linked system and related studies on
organometallic alkynylsilanes are very scarce [6].
The development of synthetic methodologies towards
transition metalÁ
shown tremendous progress following the initial reports
on Group 10 metalÁacetylide polymers [1]. Since then,
various synthetic routes have been devised by a number
of research groups to afford organometallic acetylide
molecules of other metal groups and there has been a
burgeoning range of ligands and metals incoporated
into these p-conjugated systems [2]. Rigid-rod conju-
gated organometallic systems of the form [Á
CÁRÁCꢀCÁ
via organic moieties impart interesting electronic and
optical properties with potential technological applica-
tions [2]. A detailed understanding of structure-property
relationships in these compounds is essential for full
exploitation of these materials. One general approach to
/
acetylide oligomers and polymers has
/
3
Although sp -silicon unit is generally not as good as
2
sp- or sp -carbon structural motif in facilitating electro-
/
M(L) Cꢀ
/
x
nic conjugation, recent studies demonstrate that delib-
erate inclusion of conjugation-interrupting units shows
good potential in improving the resulting optical and
photophysical properties of these conjugated com-
pounds [3d,7]. As part of our continuing study into
the properties of organometallic alkynyls [2h,2i,3c,3d,8],
a comprehensive program was therefore launched re-
cently in our laboratory to develop synthetic pathways
to a new class of organic and metalloorganic conjugated
materials containing alkynylsilane units [9]. Here, we
present the results on the first synthesis, characterization
/
/
/
/
]n containing transition metal sites linked
*
Corresponding author. Tel.: ꢁ
348.
E-mail address: rwywong@hkbu.edu.hk (W.-Y. Wong).
/
852-3411-7074; fax: ꢁ852-3411-
/
7
0
022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00003-2

28
W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á34
/
and electrochemistry of a series of soluble Group 8
metal-containing alkynylsilanes and alkynyldisiloxanes.
terminal acetylide complexes of ruthenium and osmium,
trans-[(dppm) ClMCꢀCSi(Ph) CꢀCH] (MꢀRu 1; Os
CSi(Me)2ÁOÁSi(Me) Cꢀ
Ru, 3; Os, 4), were made using the established
/
/
/
2
2
The crystal structures of trans-[(dppm) ClMCꢀ
/
CSi-
2) and trans-[(dppm) ClMCꢀ
/
/
/
/
2
2
2
(
Ph) Cꢀ
/
CH] (Mꢀ
/
Ru, Os) are presented which repre-
CH] (Mꢀ
/
2
sent the first structurally characterized examples of
ruthenium(II) and osmium(II) acetylide complexes
linked by a SiPh group.
method through the formation of vinylidene intermedi-
ates followed by deprotonation [11]. The reactions of
2
cis-[M(dppm) Cl ] (MꢀRu, Os) with one equivalent of
2
2
/
I and two equivalents of NaPF produced vinylidene
6
complexes which were not isolated but instead, were
deprotonated in situ by one equivalent of 1,8-diazabi-
cyclo[5.4.0]undec-7-ene (DBU) to give complexes 1 and
2
. Results and discussion
2
. In a similar manner, compounds 3 and 4 have been
prepared via the NaPF6ÁDBU route involving cis-
M(dppm) Cl ] (MꢀRu, Os) and II in a 1:1 stoichio-
2
.1. Synthesis
/
[
/
The synthesis of the ligands, diethynyldiphenylsilane
2
2
metry. Efforts to synthesize the homometallic dinuclear
di-yne complexes using two molar equivalents of cis-
(
I) and 1,3-diethynyltetramethyldisiloxane (II), was
carried out by modifications of the literature procedures
Scheme 1) [10]. Reaction of the Grignard reagent HCꢀ
CMgCl with Ph SiCl or ClSi(Me) ÁOÁSi(Me) Cl in
[
M(dppm) Cl ] under ambient conditions were unsuc-
2 2
(
/
cessful, presumably due to the steric bulk between the
terminal metal groups with bulky phosphine rings. All
these newly synthesized Group 8 metal complexes were
purified by passage of the respective crude product
through a short alumina column and isolated as air-
stable light yellow fine powders in reasonably good
yields. They show good solubility in chlorinated solvents
/
/
2
2
2
2
THF afforded crude products I and II, respectively.
Compound I was purified by column chromatography
on silica to give an off-white solid whereas II was
collected by vacuum distillation to furnish a colorless
volatile liquid which should cautiously be stored below
4
complexes of ruthenium(II) and osmium(II) containing
alkynylsilane ligands are also shown in Scheme 1. New
8C. The reactions leading to the new s-acetylide
1
31
1
and have been characterized by IR, H- and P{ H}-
NMR spectroscopies and positive FAB-mass spectra.
/
6 2 2 2 2
Scheme 1. (i) HCꢀCMgCl, THF; (ii) NaPF , CH Cl ; (iii) DBU, CH Cl .

W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á
/34
29
2
.2. Spectroscopic properties
Table 1
Electrochemical data for complexes 1Á
/
4 and cis-[M(dppm)
2
Cl
2
] (Mꢀ
/
Ru, Os) in CH
2 2
Cl
The starting precursors I and II both show IR
absorptions assignable to the Cꢀ
/
C and Cꢀ
/
CH stretch-
a
Complex
E
1/2 (V)
1
ing vibrations. The H-NMR resonances arising from
the phenyl (for I) and methyl (for II) protons are clearly
1
2
3
4
0.11
1
3
ꢂ
/
0.11
0.01
0.21
0.41
0.27
identified and each of them shows two strong C-NMR
signals for the two distinct sp carbons, in accordance
ꢂ
/
with their formulations. For 1Á
/
4, characteristic n(Cꢀ
/C)
2 2
cis-[Ru(dppm) Cl ]
bands are observed in their IR spectra in the range
ꢂ1
2 2
cis-[Os(dppm) Cl ]
1
acetylenic group is discernible from the IR spectral
983Á/2035 cm . The presence of an uncoordinated
a
100 mV sꢂ1, half-wave potential values E1/2
Scan rateꢀ
/
ꢀ/
(Epa
ꢁ/
E
pc)/2 for reversible oxidation, where Epa and Epc are the anodic and
cathodic peak potentials, respectively.
ꢂ1
peaks at ca. 3284 cm
1
due to n(ꢀ
/CH) in all cases. In
their H-NMR spectra, the proton signal stemming
from the terminal acetylene appears as a sharp peak
also indicate that the ruthenium centre acts as a better
acceptor than the osmium counterpart, probably owing
within the short range d 2.3Á2.5 and resonances
/
characteristic of the CH group in the bridging phos-
phines are apparent. Two well-defined methyl signals
which are separated by about 0.6 ppm are evident in the
to better stabilization of the ꢁ
/
3 state by osmium and
2
this phenomenon was also observed for the complexes
5
5
[(h -C H )Fe(h -C H )Cꢀ
/
CM(dppm) Cl] (MꢀRu, Os)
/
5
5
5
4
2
1
H-NMR spectra of 3 and 4 and each of them is
[12].
integrated as six protons. Complexes 1Á4 show room-
/
3
1
1
temperature P{ H}-NMR spectra consistent with the
trans geometry of the two dppm ligands and the spectral
data fully agree with the solid state structures (vide
2.4. Molecular structures
3
1
1
infra). The P{ H} chemical shifts for 1Á
/
4 compare
Yellow block-shaped crystals of good quality for 1
and 2 were obtained by allowing their respective
well with those reported for other mononuclear ruthe-
nium and osmium s-acetylide complexes [11] and they
are rather insensitive to the variation of the central
organic linker groups. The FAB-mass spectra of com-
solutions in CH Cl Áhexane to stand in crystallization
/
2
2
vials for 1 day. Both compounds 1 and 2 are isostruc-
tural and conform to the same space group with two
crystallographically independent molecules per asym-
metric unit. The structures of one molecule of 1 and 2
are depicted in Figs. 1 and 2, respectively, and the
important molecular dimensions are listed in Table 2.
To our knowledge, complexes 1 and 2 are the first
structurally characterized examples of Group 8 metal
pounds 1Á
/
4 all exhibit small molecular ion peaks and
comparatively more intense peaks attributable to the
ꢁ
daughter ions [M(dppm)2] (Mꢀ
tion by the loss of Ph group was also observed in each
case. Rupture of the metalÁphosphorus bond (for 1Á4)
and the siliconÁoxygen bond (for 3 and 4) is not a major
/
Ru, Os). Fragmenta-
/
/
/
3
fragmentation pattern for these complexes under the
experimental conditions.
mono-acetylide compounds bearing an inorganic sp -
silicon bridging unit. Each molecule possesses an overall
C symmetry with the mirror plane passing through the
s
2
.3. Electrochemistry
metal atom and bisecting each dppm ligand. Both the
chlorine atom and the alkynyl unit lie within the mirror
plane.
The electrochemical properties of complexes 1Á
/4 were
studied in CH Cl at room temperature by means of
cyclic voltammetry and the redox data are collected in
Table 1 together with those for the starting metal
The crystal structures of 1 and 2 consist of discrete
monomer molecules with the corresponding metal atom
coordinated in a trans deposition to two chelating dppm
ligands and the coordination sphere around the metal is
completed by one chlorine and one alkynylsilane ligands
in a trans arrangement. The coordination at the
ruthenium (or osmium) is distorted octahedral, with
2
2
precursors cis-[M(dppm) Cl ] (Mꢀ
/
Ru, Os). For 1Á
each shows a quasi-reversible oxidation event due to the
M(II)0M(III) process (MꢀRu, Os). The half-wave
potentials of ruthenium in 1 and 3 and osmium in 2 and
are considerably less anodic than those of the metal
centres in cis-[M(dppm) Cl ] (MꢀRu, Os). This can be
/
4,
2
2
/
/
4
angles between cis donor atoms in the range 69.41(4)Á
111.06(5)8 (69.08(6)Á111.58(6)8) and those between
trans atoms in the range 176.53(5)Á178.16(14)8
(176.04(7)Á177.84(19)8). The principal contractions
from 908 are due to the ‘bite’ of the chelating dppm
groups. The metalÁphosphorus bonds are typical at
2.3271(14)Á2.3768(13) (for 1) and 2.3353(19)Á
2.3723(17) (for 2), while the metalÁchlorine distances
/
/
/
2
2
attributed to the increased electron density in the metal
vicinity induced by the unsaturation of the ethynyl
bridge, which renders the oxidation easier. The presence
of an electron-rich oxygen atom in the disiloxane bridge
in 3 and 4 lowers the electrode potential values by ca.
/
/
/
/
/
0
.10 V as compared to 1 and 2, respectively. Our results
/

30
W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á34
/
Fig. 1. A perspective view of one molecule of 1, with thermal ellipsoids shown at the 25% probability level. Hydrogen atoms and all labels on phenyl
carbon atoms were omitted for clarity.
at 2.5034(14)Á
/
2.5041(13) (for 1) and 2.5070(18)Á
/
structures of the type trans-[(dppm) ClMCꢀ
/
CArCꢀ
/
2
2
.5119(17) (for 2) are in good agreement with those
CR] [11c,12,13].
found in other structurally characterized ruthenium and
osmium mono-chloro acetylide complexes [11c,12,13].
In both cases, the metal-coordinated Cꢀ
/
C bond lengths
C(52) 1.225(7), 1.213(6) A in 1 and 1.225(9),
˚
3. Concluding remarks
(
C(51)Á
/
˚
.229(9) A in 2) are a common feature of metal-acetylide
1
In summary, we have widened our scope to form a
new series of rigid-rod s-acetylide complexes of ruthe-
nium(II) and osmium(II) containing functionalized silyl
moieties as the linking unit and have structurally
characterized the first examples of such complexes.
These complexes exhibit reversible redox couple attri-
butable to the M /M oxidation. We are currently
attempting to develop new synthetic methodologies in
the quest for a novel class of silyl-bridged heterometallic
s-bonding and the CꢀCH bond (C(65)ÁC(66) 1.129(7),
/
/
˚ ˚
.105(7) A in 1 and 1.167(10), 1.160(9) A in 2) appears
slightly shorter because of the libration effect frequently
1
observed in terminal acetylene unit [8a,9a,14]. The
˚
C(52) single bond lengths (average 1.790 A in 1,
Si(1)Á
/
˚
1.780 A in 2) are notably shorter than the other Si(1)Á
C(65) bond (average 1.847 A in 1, 1.848 A in 2),
/
II
III
˚
˚
3
suggesting that the sp -silicon atom partially breaks p-
conjugation along the chain. The Cl(1)Á
/
M(1)Á
/
C(51)Á
/
alkynyl complexes starting from compounds 1Á4 or
/
C(52) and Si(1)ÁC(65)ÁC(66) fragments are essentially
/
/
alike. Analysis of the physical and optical properties of
the resulting complexes to assess the extent of conjuga-
tion in the main chain and a comparison with those for
the corresponding complexes of Group 10 metals and
other complexes of Group 8 having (hetero)aromatic
linear in both complexes. There are no apparent short
intermolecular contacts between adjacent molecules in
these crystals. All of the remaining structural parameters
are comparable to those observed for other crystal

W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á
/34
31
Fig. 2. A perspective view of one molecule of 2, with thermal ellipsoids shown at the 25% probability level. Hydrogen atoms and all labels on phenyl
carbon atoms were omitted for clarity.
spacers are also worthy of study and will be pursued in
our laboratory.
4. Experimental
4.1. General procedures
Table 2
All reactions were carried out under a nitrogen
˚
Selected bond lengths (A) and bond angles (8) for complexes 1 and 2
atmosphere with the use of standard inert atmosphere
and Schlenk techniques, but no special precautions were
taken to exclude oxygen during work-up. Solvents were
predried and distilled from appropriate drying agents
1
2
Molecule 1 Molecule 2 Molecule 1 Molecule 2
[
15]. All chemicals, unless otherwise stated, were
Bond lengths
M(1)Á
M(1)Á
M(1)Á
M(1)Á
M(1)Á
M(1)Á
C(51)Á
/
P(1)
P(2)
P(3)
P(4)
Cl(1)
C(51)
2.3531(13) 2.3480(13) 2.3628(18) 2.3662(18)
2.3271(14) 2.3439(13) 2.3723(17) 2.3719(18)
2.3634(14) 2.3661(13) 2.3463(19) 2.3528(18)
2.3768(13) 2.3706(13) 2.3473(18) 2.3353(19)
2.5034(14) 2.5041(13) 2.5119(17) 2.5070(18)
obtained from commercial sources and used as received.
The compounds cis-[M(dppm) Cl ] were prepared by
/
2
2
/
the reported procedures [16]. Infrared spectra were
recorded as CH Cl solutions in a CaF cell (0.5 mm
/
2
2
2
/
path length) on a Perkin Elmer Paragon 1000 PC or
Nicolet Magna 550 Series II FTIR spectrometer. NMR
spectra were measured in CDCl on a JEOL EX270 or a
/
1.990(5)
1.225(7)
1.791(5)
1.847(7)
1.129(7)
2.003(5)
1.213(6)
1.788(5)
1.846(6)
1.105(7)
2.001(7)
1.225(9)
1.786(8)
1.846(8)
1.167(10)
2.010(7)
1.229(9)
1.774(8)
1.849(9)
1.160(9)
/
C(52)
Si(1)Á/C(52)
3
Si(1)Á/C(65)
1
Varian Inova 400 MHz FT NMR spectrometer, with H
NMR chemical shifts quoted relative to SiMe and
C(65)Á
Bond angles
P(1)ÁM(1)Á
P(2)ÁM(1)Á
Cl(1)Á
M(1)Á
Si(1)ÁC(52)Á
C(52)ÁSi(1)Á
Si(1)ÁC(65)Á
/
C(66)
4
31
1
P{ H} chemical shifts relative to an 85% H PO
3
4
/
/
P(4)
P(3)
110.56(5)
108.82(5)
111.06(5)
108.60(5)
108.71(6)
111.58(6)
109.32(6)
111.03(6)
external standard. Fast atom bombardment mass spec-
tra were recorded on a Finnigan MAT SSQ710 mass
spectrometer. Cyclic voltammetry experiments were
done with a Princeton Applied Research (PAR) model
273A potentiostat. A conventional three-electrode con-
figuration consisting of a glassy-carbon working elec-
/
/
/M(1)Á
/
C(51) 178.16(14) 177.46(13) 177.37(19) 177.84(19)
/C(51)Á
/
C(52) 177.5(4)
174.4(4)
166.4(5)
109.0(2)
175.5(6)
175.5(6)
163.8(7)
109.5(3)
178.4(8)
177.9(6)
163.4(6)
107.5(3)
172.8(8)
/
/
C(51) 165.6(5)
C(65) 106.4(2)
C(66) 173.4(6)
/
/
/
/

32
W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á34
/
trode, a Pt-wire counter electrode and a Ag/AgNO3
reference electrode (0.1 M in acetonitrile) was used. The
solvent in all measurements was deoxygenated CH Cl
were stirred for 6 h at r.t. The resulting light yellow
solution was filtered through a pad of Celite to remove
any excess NaPF and NaCl by-product, and DBU (7.60
6
2
2
and the supporting electrolyte was 0.1 M [Bu N]PF .
4
mg, 0.05 mmol) was added. After stirring for 3 h, the
solvent was removed in vacuo. The residue was dis-
6
Ferrocene was added as a calibrant after each set of
measurements and all potentials reported were quoted
with reference to the ferrocene-ferrocenium couple
solved in Et O and filtration through a short alumina
2
column using pure Et O as eluent afforded complex 1 as
2
(
taken as E1/2
ꢀ
/
ꢁ
/
0.17 V relative to Ag/AgNO3).
.2. Preparations of compounds
.2.1. Synthesis of HCꢀ
a pale yellow solid in 74% yield (42.0 mg). Recrystalliza-
tion of 1 was achieved from an evaporated hexaneÁ
/
4
4
CH Cl solution at r.t., giving light yellow crystals in a
2
2
pure form. IR (CH Cl ): 3284 n(ꢀ
/
CH), 2032, 1989 n(Cꢀ
/
2
2
ꢂ1
1
/
CSi(Ph) Cꢀ
/
CH (I)
C) cm . H-NMR (CDCl ): d 2.48 (s, 1H, Cꢀ
/
CH),
2
3
3
A 0.5 M THF solution of HCꢀ
/
CMgCl (50 cm , 25.0
4.75 (m, 2H, CH ), 4.92 (m, 2H, CH ) and 6.96Á
/7.57 (m,
2
2
3
1
1
mmol, Aldrich) was added dropwise into a solution of
3
Ph SiCl (2.5 g, 10.0 mmol) in the same solvent (5 cm )
50H, Ph). P{ H}-NMR (CDCl ): d ꢂ
/
4.61. FABMS:
ꢁ
3
ꢁ
ꢁ
m/z 1137 [M ], 1102 ([Mꢂ
/
Cl] ), 1060 ([MꢂPh] ) and
/
2
2
ꢁ
at room temperature (r.t.) under nitrogen. The mixture
was heated to 30Á40 8C and stirred for 3 h before all the
871
(CH Cl ): l
([Mꢂ
/
Clꢂ
(o ꢃ
/
Cꢀ
/
CSi(Ph) Cꢀ
/
CH] ).
ꢂ1
UVÁvis
/
2
ꢂ4
3
dm mol
cmꢂ1) 230 (7.4)
/
/
10
2
2
max
volatile components were removed under reduced pres-
sure. The residue was taken up in Et O and filtered
and 266 (5.0). Anal. Found: C, 69.50; H, 4.68. Calc. for
C H ClP RuSi: C, 69.74; H, 4.88%.
2
66 55
4
through a pad of Celite. The filtrate was concentrated
and subjected to column separation on silica using a
mixture of Et O and hexane (1:9, v/v) as eluent. From
4.2.4. Synthesis of trans-[(dppm) ClOsCꢀ
/
CSi(Ph) Cꢀ
/
2
2
CH] (2)
To a solution of cis-[Os(dppm) Cl ] (103 mg, 0.10
2
the major band, the title compound was collected as an
off-white solid in 97% yield (2.3 g). IR (CH Cl ): 3263
2
2
3
mmol) in 80 cm of CH Cl , compound I (23.2 mg, 0.10
2
2
2
2
ꢂ1
1
n(ꢀ
/
CH), 2032 n(Cꢀ
s, 2H, CꢀCH), 7.39Á
m, 4H, Ph). C-NMR (CDCl ): d 83.37 (Cꢀ
/
C) cm . H-NMR (CDCl ): d 2.75
mmol) and NaPF (33.6 mg, 0.20 mmol) were added.
6
3
(
(
(
/
/
7.48 (m, 6H, Ph) and 7.74Á
C), 97.36
CH), 128.19, 130.60, 131.25, 134.74 (Ph). FABMS:
/
7.79
The reaction mixture was allowed to react for 6 h at
ambient temperature. The solution which changed from
yellow to greenish-yellow was filtered through Celite.
After the addition of DBU (15.2 mg, 0.10 mmol), the
solution turned light yellow at once and the mixture was
allowed to stir for an additional 3 h. The solvent was
evaporated to dryness and the residue was taken up in
1
3
/
3
Cꢀ
/
ꢁ
m/z 232 [M ]. Anal. Found: C, 82.60; H, 5.02. Calc. for
C H Si: C, 82.71; H, 5.21%.
1
6
12
4
.2.2. Synthesis of HCꢀ
II)
To a solution of ClSi(Me) Á
/
CSi(Me)2Á
/
OÁ
/
Si(Me) Cꢀ
/
CH
2
(
Et O and then chromatographed on a short alumina
2
/
OÁ
/
Si(Me) Cl (1.0 g, 5.0
2
column eluting with Et O, resulting in the isolation of
2
2
3
mmol) in pre-dried THF (5 cm ), 0.5 M THF solution of
bright yellow product 2 (80.0 mg, 65%). Similar to 1, this
compound can be purified by recrystallizing from a
3
HCꢀ
at r.t. under nitrogen. The mixture was heated to 40Á
0 8C and stirred for a period of 3 h. The solution was
/
CMgCl (25 cm , 12.5 mmol) was added dropwise
/
hexaneÁ
(ꢀCH), 2031, 1983 n(Cꢀ
2.46 (s, 1H, CꢀCH), 5.27 (m, 2H, CH ), 5.46 (m, 2H,
CH ) and 6.97Á
/
CH Cl solution at r.t. IR (CH Cl ): 3284 n
2 2 2 2
ꢂ1
1
5
/
/C) cm . H-NMR (CDCl ): d
3
3
gently concentrated to about 10 cm under reduced
pressure and then filtered through a short layer of silica
/
2
3
1
1
/
7.52 (m, 50H, Ph). P{ H}-NMR
2
ꢁ
to remove the Mg residue using pentaneÁ
/
Et O (1:1, v/v)
2
(CDCl ): d ꢂ
/
46.21. FABMS: m/z 1226 [M ], 1149
ꢁ
3
ꢁ
as eluent. The filtrate was concentrated in vacuo gently
without heating to give a volatile and colorless liquid in
([Mꢂ
/
Ph] ), 1037 ([Mꢂ
/
Clꢂ
/
2Ph] ) and 960 ([Mꢂ
/
Clꢂ
/
ꢁ
CꢀCSi(Ph) Cꢀ
/
/
CH] ). UVÁ
/
vis (CH Cl ): l
(o ꢃ
/
2
2
2
max
ꢂ4
3
dm mol
ꢂ1
ꢂ1
9
4% yield (0.86 g) which should be stored below 4 8C.
10
cm ) 230 (6.7) and 254 sh (3.8).
ꢂ1
1
C) cm . H-
IR (CH Cl ): 3284 n(ꢀ
/
CH) 2037 n(Cꢀ
/
Anal. Found: C, 64.44; H, 4.39. Calc. for C H ClP -
66 55 4
2
2
NMR (CDCl ): d 0.31 (s, 12H, Me) and 2.42 (s, 2H, Cꢀ
/
OsSi: C, 64.67; H, 4.52%.
3
1
3
CH). C-NMR (CDCl ): d 1.89 (Me), 88.96 (Cꢀ
/
C) and
CH). FABMS: m/z 182 [M ]. Anal. Found:
C, 52.26; H, 7.48. Calc. for C H OSi : C, 52.69; H,
3
ꢁ
9
2.33 (Cꢀ
/
4.2.5. Synthesis of trans-[(dppm) ClRuCꢀ
/
CSi(Me)2-
2
OÁ
/
Si(Me) Cꢀ
/
CH] (3)
8
14
2
2
7
.74%.
cis-[Ru(dppm) Cl ] (47.0 mg, 0.05 mmol) was added
2
2
to HCꢀ
mmol) in CH Cl (40 cm ) in the presence of NaPF
6
/
CSi(Me)2Á
/
OÁ
/
Si(Me) Cꢀ
/
CH (II, 9.10 mg, 0.05
2
3
4
CH] (1)
.2.3. Synthesis of trans-[(dppm) ClRuCꢀ
/
CSi(Ph) Cꢀ
/
2
2
2
2
(16.8 mg, 0.10 mmol) and the mixture was stirred for 24
h. The resultant faintly yellow vinylidene solution was
filtered and DBU (7.60 mg, 0.05 mmol) was added.
After the solution was stirred for a further 3 h, the
A mixture of cis-[Ru(dppm) Cl ] (47.0 mg, 0.05
2
2
mmol), HCꢀ
/
CSi(Ph) Cꢀ
/CH (I, 11.6 mg, 0.05 mmol)
2
3
and NaPF (16.8 mg, 0.10 mmol) in CH Cl (40 cm )
6
2
2

W.-Y. Wong et al. / Journal of Organometallic Chemistry 671 (2003) 27Á
/34
33
solvent was removed and the residue dissolved in Et O
2
Table 3
Summary of crystal structure data for complexes 1 and 2
was subjected to a short silica column using the same
solvent as eluent. A light yellow solid of 3 was collected
1
2
in 49% yield (26.6 mg). IR (CH Cl ): 3284 n(ꢀ
/
CH),
2
2
ꢂ1
1
Empirical formula
Molecular weight
C
66
H
55ClP
4
RuSi
C
66 4
H55ClOsP Si
2
034, 1993 n(Cꢀ
/
C) cm . H-NMR (CDCl ): d ꢂ
/
0.51
3
1136.59
1225.72
(
(
s, 6H, Me), 0.11 (s, 6H, Me), 2.35 (s, 1H, Cꢀ
/
CH), 4.91
3
Crystal size (mm )
0.28ꢃ0.18ꢃ
Monoclinic
P2 /n
/
/
0.16 0.32ꢃ0.23ꢃ0.18
/
/
3
1
7.54 (m, 40H, Ph). P{ H}-
1
m, 4H, CH ) and 7.13Á
/
2
Crystal system
Space group
Unit cell dimensions
Monoclinic
P2 /c
ꢁ
NMR (CDCl ): d ꢂ
/
4.71. FABMS: m/z 1085 [M ],
3
1
1
ꢁ
1
008 ([Mꢂ
/
Ph] ) and 869 ([Mꢂ
/
Clꢂ
vis (CH Cl ): l
max
/
Cꢀ
/
CSi(Me)2Á
/
OÁ
/
ꢁ
ꢂ4
a ( A˚ )
11.9173(15)
22.976(3)
41.205(5)
11.9087(6)
22.9827(11)
41.113(2)
Si(Me) CꢀCH] ). UVÁ
/
/
(o ꢃ10
/
2
2
2
˚
b (A)
3
ꢂ1
ꢂ1
dm mol cm ) 230 (6.5) and 269 (3.8). Anal. Found:
C, 63.98; H, 5.18. Calc. for C H ClOP RuSi : C,
˚
c (A)
5
8
57
4
2
a (8)
b (8)
g (8)
6
4.11; H, 5.29%.
98.228(2)
98.2440(10)
3
˚
U (A )
11166(2)
1.352
8
11136.1(10)
1.462
8
D
Z
calc (g cmꢂ3
)
4
.2.6. Synthesis of trans-[(dppm) ClOsCꢀ
/
CSi(Me)2Á
/
2
m (MoÁ
F(000)
u Range (8)
/K
a
) (mmꢂ1
)
0.506
4688
2.516
4944
OÁ
/
Si(Me) Cꢀ
/
CH] (4)
2
Following the same procedures as for 3 above, the
desired product 4 was obtained as a bright yellow
powder in 51% yield (30.0 mg) from cis-[Os(dppm) Cl ]
1.34Á
65778
25145
/27.51
1.34Á27.51
65816
25173
/
Reflections collected
Unique reflections
2
2
R
int
0.0636
12491
0.0896
12071
(
51.5 mg, 0.05 mmol) and II (9.10 mg, 0.05 mmol)
C)
Observed reflections
I ꢀ2s(I)]
No. of parameters
, wR [I ꢀ2s(I)]
R , wR (all data)
instead. IR (CH Cl ): 3284 n(ꢀ
cm . H-NMR (CDCl ): d ꢂ
/
CH), 2035, 2001 n(Cꢀ
/
2
2
[
/
ꢂ1
1
/
0.51 (s, 6H, Me), 0.09 (s,
1316
1316
3
6
H, Me), 2.33 (s, 1H, Cꢀ
/
CH), 5.42 (m, 4H, CH ) and
2
R
1
2
/
0.0560, 0.1471
0.1275, 0.1913
0.718
0.0463, 0.0852
0.1294, 0.1139
0.763
3
7.48 (m, 40H, Ph). P{ H}-NMR (CDCl ): d
1
1
1
2
7
.13Á
/
3
2
ꢁ
ꢁ
Goodness-of-fit on F
Residual extrema in final
˚
difference map (e A
ꢂ
/
46.64. FABMS: m/z 1175 [M ], 1098 ([MꢂPh] )
/
0.826 to ꢂ
/
0.799 0.867 to ꢂ1.071
/
ꢁ
and 961 ([Mꢂ
/
Clꢂ
/
Cꢀ
max
/
CSi(Me)2Á
/
OÁ
/
Si(Me) Cꢀ
/
CH] ).
ꢂ1
ꢂ3
2
)
ꢂ4
3
dm mol
ꢂ1
UVÁvis (CH Cl ): l
/
(o ꢃ/10
cm
30 (1.2) and 255 sh (7.0). Anal. Found: C, 59.01; H,
)
2
2
2
5
6. Supplementary material
.08. Calc. for C H ClOOsP Si : C, 59.25; H, 4.89%.
2
5
8
57
4
Crystallographic data (comprising hydrogen atom
coordinates, thermal parameters and full tables of
bond lengths and angles) for the structural analysis
have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC nos. 197039 and 197040.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
5
. Crystallography
Single crystals of 1 and 2 suitable for X-ray crystal-
lographic analyses were chosen and mounted on a glass
fiber using epoxy resin. Crystal data and other experi-
mental details are summarized in Table 3. The diffrac-
tion experiments were carried out at 293 K on a Bruker
AXS SMART 1000 CCD area-detector diffractometer
Cambridge CB2 1EZ, UK (Fax: ꢁ44-1223-336033; e-
/
mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
using graphite-monochromated Mo-K radiation (lꢀ
/
a
.71073 A). At the end of data collection, no crystal
˚
0
Acknowledgements
decay was observed. The collected frames were pro-
cessed with the software SAINT [17a], and an absorption
correction was applied (SADABS) [17b] to the collected
reflections. The structures were solved by direct methods
and expanded by difference Fourier syntheses using the
software SHELTXL [18]. Structure refinements were made
Financial support from the Hong Kong Research
Grants Council (HKBU 2054/02P) is gratefully ac-
knowledged.
2
on F by the full-matrix least-squares technique. In each
case, all the non-hydrogen atoms were refined with
anisotropic displacement parameters. The hydrogen
atoms were placed in their ideal positions and not
refined.
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