Synthesis and structural studies of Ti-Ru polymetallic systems

Article abstract of DOI:10.1016/S0022-328X(00)00219-9

The reaction of the titanocene monophosphines 1 and 2 with the dimer [(p-cymene)RuCl₂]₂ give the heterobimetallic compounds (p-cymene)[(η⁵-C₅H₄)(μ-η ⁵:η¹-C₅H₄PPh ₂)TiCl₂]RuCl₂ and (p-cymene)[(η⁵-C₅H₄)(μ-η ⁵:η¹-C₅H₄CH₂CH ₂PPh₂)TiCl₂]RuCl₂, respectively. Both structures have been confirmed by X-ray diffraction. By using same procedure, the synthesis of a trimetallic complex Ru-Ti-Ru has been achieved.

Full text of DOI:10.1016/S0022-328X(00)00219-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 605 (2000) 151–156
Synthesis and structural studies of TiꢀRu polymetallic systems
Pierre Le Gendre, Philippe Richard, Claude Mo¨ıse *
Laboratoire de Synthe`se et d’Electrosynthe`se Organome´talliques, LSEO-UMR 5632, Uni6ersite´ de Bourgogne, Faculte´ des Sciences Gabriel,
6 bd Gabriel, 21000 Dijon, France
Received 18 February 2000; accepted 7 April 2000
Abstract
The reaction of the titanocene monophosphines 1 and 2 with the dimer [(p-cymene)RuCl2]2 give the heterobimetallic compounds
(p-cymene)[(h5-C5H4)(m-h5:h1-C5H4PPh2)TiCl2]RuCl2 and (p-cymene)[(h5-C5H4)(m-h5:h1-C5H4CH2CH2PPh2)TiCl2]RuCl2, respec-
tively. Both structures have been confirmed by X-ray diffraction. By using same procedure, the synthesis of a trimetallic complex
RuꢀTiꢀRu has been achieved. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Titanocene; Ruthenium; Heterobimetallic complexes
homogeneous catalysis remains fantastic. Indeed, a co-
operative work by the two metal centers in the complex
would lead to new catalytic systems with unique reac-
tivity [3]. We have therefore concentrated our efforts on
the synthesis and study of heterobimetallic complexes in
which both metal fragments are already well-known in
catalysis field. Titanocenes are of considerable interest
as cocatalysts for the polymerisation of a-olefins [4].
The catalytic performance of RuCl2(arene) complexes
has been demonstrated in many kind of reactions [5]. In
attempts to examine such type of catalytic activity we
studied the complexation of bent titanocene metallo-
ligands with the dimer [(p-cymene)RuCl2]2.
1. Introduction
Numerous studies have been directed towards the
synthesis of early–late heterobimetallic complexes [1].
Surprisingly, only few reports have been reported about
their catalytic behavior [2]. However, their potential in
The use of heterodifunctional ligands as
−C5H4(CH2)nPPh2 is a very convenient method to link
dissimilar transition metals, and in this way, allowed
the access to many polymetallic systems [6]. The metal
fragments are held together through the bridging ligand
with or without a direct metalꢀmetal bond. Here we
report the synthesis of two TiꢀRu bimetallic and one
RuꢀTiꢀRu trimetallic complexes by using this strategy.
Scheme 1.
2. Discussion and results
Scheme 2.
Previous studies in our laboratory gave rise to a
straightforward access to bent titanocene mono and
diphosphines [6a,b]. The monophosphines 1 and 2 were
prepared according to an earlier method involving the
* Corresponding author.
E-mail address: claude.moise@u-bourgogne.fr (C. Mo¨ıse).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00219-9

152
P. Le Gendre et al. / Journal of Organometallic Chemistry 605 (2000) 151–156
Fig. 1. An ORTEP [8] view of the compound 3 with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms and solvate molecules
are omitted for clarity.
reaction of the lithium (diphenylphosphino)- or
((diphenylphosphino)ethyl) cyclopentadienide with
CpTiCl3 (Scheme 1) [6a].
Single crystals of 3 and 4, suitable for X-ray diffrac-
tion, were obtained by layering technique. ORTEP views
of the compounds 3 and 4 are respectively shown in
Figs. 1 and 2. The Crystallographic Parameters are
reported in Table 1 and the bond distances and angles
in Table 2.
Both structures consist in two fragments: a dichloro
titanocene moiety and a (p-cymene)RuCl2 moiety. The
linkage is achieved either by a direct bonding of the
phosphorus atom to one carbon atom of a Cp ring for
3 or by an ethylene spacer between the Cp ring and the
phosphorus atom for 4.
The geometries of the CpCp%TiCl2 fragments are
typically tetrahedral in both structures with similar
structural parameters. These two titanocene moities
show only a difference in the position of the sub-
stituents held by the cyclopentadienyl ring: in 4, the
uncluttered methylene substituent is located in the open
side of the bent metallocene and lies above the TiCl2
1
The H-NMR and 31P-NMR chemical shifts of these
two phosphines are consistent with the phosphine lig-
ands not coordinated to a metal atom. Both are stable
under argon and can be handled easily. Despite these
two ligands are made of bent titanocene and
diphenylphosphine entities, the coordinative ability of
both phosphorus atoms might be different. Indeed, the
phosphorus atom in 2 will be in a less hindered envi-
ronment than in 1. Moreover, the alkyl bridge might
prevent any electron attractive effect of the titanium
center on the phosphorus atom.
Organic phosphines can easily cleave the chloride
bridges of the dimer [(p-cymene)RuCl2]2 to lead to
(p-cymene)RuCl2PR3 complexes [7]. On the basis of
this result we carried out experiments by using the
metallophosphines
1 and 2 with the dimer [(p-
cymene)RuCl2]2 in benzene. The bimetallic complexes 3
and 4 were obtained with high yields after 4 h at room
temperature (Scheme 2).
fragment,
the
dihedral
angle
between
the
Ct(3)ꢀCt(2)ꢀC(12) plane and the Ct(2)ꢀTiCt(3) one is
only 8°. In contrast, for the compound 3, the bulky
PPh2 substituent is rotated from the previous bisecting
position leading to a dihedral angle defined as above
equal to 144°. While in 3 the carbon atom attached to
the Cp ring lies in the Cp plane, in the compound 4, the
The characterisation of 3 and 4 was based upon
elemental analysis, 1H-NMR and 31P-NMR spectro-
scopic data. The 31P-NMR chemical shifts of 3 and 4 of
15.1 and 21.3 ppm correspond to a downfield shift of
1
,
31 and 39 ppm relatively to free ligands. The H-NMR
phosphorus atom lies 0.39 A above this plane.
spectra of 3 and 4 displays 0.2–0.5 ppm upfield shift of
the p-cymene protons resonances compared to the
ruthenium dimer precursor. A downfield shift of the
diphenylphosphine ortho-protons was observed. These
results are indicative of the coordination of the phos-
phorus atoms to the ruthenium metal.
In both structures, the arene ruthenium moities
present a three-legged piano stool structure with struc-
tural parameters similar to those observed for 19 (h6-
arene)RuCl2(PPh2R) structures (among these, three
include both ferrocene and (h6-arene)RuCl2 linked by a
diphenyl phosphido bridge [9]). In these complexes the

P. Le Gendre et al. / Journal of Organometallic Chemistry 605 (2000) 151–156
153
ruthenium atoms. These results are closely similar to
those obtained by Graham et al. for titane–rhodium
and titane–palladium complexes [6f].
3. Conclusion
We report the preparation of two heterobimetallic
complexes containing both titanocene and rutheniu-
m(arene) fragments. These syntheses involve the prepa-
ration of titanocene monophosphines followed by the
coordination of the phosphorus group to the ruthenium
atom. The targeted heterobimetallic complexes have
been obtained with good yields. Similar strategy al-
lowed us to synthesize a RuꢀTiꢀRu trimetallic complex
with good yield. Studies about the catalytic activity of
these new heteropolymetallic systems are currently in
progress.
Scheme 3.
mean RuꢀCl and RuꢀP distances are equal to 2.41(1)
and 2.35(2) A, respectively.
,
These results prompted us to use the same strategy
for the preparation of trimetallic complexes. The
organometallic diphosphine 5 [6a] reacts with the dimer
[(p-cymene)RuCl2]2 to give the trimetallic complex 6
isolated as a brick powder in 80% yield (Scheme 3). The
1H-NMR and 31P-NMR spectra of 6 display almost the
same chemical shifts as 4. The 31P-NMR spectrum of 6
4. Experimental
NMR spectra were recorded on a BRUKER AC200
1
1
exhibits only one singlet at +21.6 ppm. The H-NMR
(200.135 MHz for H, 81.004 MHz for 31P) spectrome-
shows an upfield shift of the p-cymene protons reso-
nances compared to the ruthenium dimer precursor as
well as a downfield shift of the diphenylphosphine
ortho-protons relatively to 5. These results are in agree-
ment with the suggested structure 6.
Our attempts to prepare a cationic ruthenium (II)
complex via removal of a chloride by NH4PF6 in order
to obtain a structure involving chelation by the two
phosphorus atoms of the ligand 5 led to oligomeric
mixtures as judged by their NMR spectra. The crystal-
lographic structure of 4 might explain this result. In-
deed, the flexibility of the alkyl bridge allowed the
ruthenium center to lie away from the titanium atom.
The two phosphorus atoms are probably located far
one each other, so as to permit coordination with the
ter. Elemental analysis was performed on a FISON EA
1108 within the laboratory. The cyclopentadienyl phos-
phine ligands Li[C5H4(CH2)nPPh2] were prepared ac-
cording to the literature method [10]. The phosphine 5
has been recently synthesized according to a modified
procedure [6e].
4.1. Complex 1
A 0.77g (2.7 mmol) sample of Li[C5H4PPh2] in 10 ml
of THF was added to 0.6 g of CpTiCl3 (2.7 mmol) in 15
ml of THF. After stirring for four hours at room
temperature (r.t.), the solvent was removed in vacuo.
The red residue was extracted with CH2Cl2, filtered
through celite, and precipitated by the addition of
Fig. 2. An ORTEP view of the compound 4 with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms and the toluene solvate
molecule are omitted for clarity.

154
P. Le Gendre et al. / Journal of Organometallic Chemistry 605 (2000) 151–156
Table 1
Ph). Anal. Calc. for C22H19Cl2PTi (433.1521): C, 61.00;
H, 4.42. Found: C, 60.55; H, 4.26%.
Crystal data and structure refinement for 3 and 4
Compound
3
4
4.2. Complex 2
Empirical formula
C
32H33Cl4PRuTi·
C34H37Cl4PRuTi.C
7H8
859.51
293(2)
Triclinic
2(CHCl3)·0.5(C6H14
1021.15
293(2)
Triclinic
)
This compound was obtained following the above
procedure but with Li[C5H4CH2CH2PPh2] (85% yield).
31P{1H}-NMR (81.004 MHz, CDCl3) l −18.08 (s,
Formula weight
T (K)
Crystal system
Space group
1
PPh2). H-NMR (200.135 MHz, CDCl3) l 2.38 (t, 2H,
(
(
P1
P1
Unit cell dimensions
CH2, J=7.9 Hz), 2.87 (dt, 2H, CH2, J=9.7, J=7.9
Hz), 6.30–6.40 (m, 4H, Cp), 7.26–7.46 (m, 10H, Ph).
Anal. Calc. for C24H23Cl2PTi (461.2057): C, 62.50; H,
5.03. Found: C, 61.60; H, 5.03%. The relatively low
percentage of carbon can be attributed to the presence
of LiCl.
,
a (A)
10.567(1)
13.038(1)
16.035(2)
101.05(1)
92.43(1)
91.82(1)
2164.5(4)
2
1030
1.567
0.71073
1.214
0.36×0.28×0.25
0.59
10.792(2)
12.915(2)
15.314(2)
83.09(1)
70.92(1)
81.31(1)
1988.3(5)
2
880
1.436
0.71073
0.918
0.30×0.30×0.22
0.62
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
4.3. Complex 5
F(000)
Dcalc (g cm−3
)
A
solution of 0.98
g
(3.47 mmol) of
,
u (A)
v (mm−1
)
Li[C5H4CH2CH2PPh2] in 15 ml of THF was added to
0.58 g (1.7 mmol) of TiCl4(THF)2 in 10 ml of THF.
After stirring for 2 h at reflux, the solution was concen-
trated and fractionated through 10 cm of Sephadex
(LH-20) to afford a red solution. Removal of the
solvent gave 5 (50% yield) as red powder. 31P{1H}-
Crystal size (mm3)
−1
,
sin(q)/umax (A
Index ranges
)
h: −12; 12
k: 0; 15
l: −18; 18
65
h: 0; 13
k: −15; 16
l: −18; 19
0
Decay (%)
Absorption
correction
RC, Reflections
collected
1
psi-scan 84–93%
psi-scan 94–98%
NMR (81.004 MHz, CDCl3) l −18.27 (s, PPh2). H-
NMR (200.135 MHz, CDCl3) l 2.31 (t, 2H, CH2,
7675
8511
IRC, independent
RC
IRCGT=IRC and 4886
[I\2|(I)]
7316 [Rint=0.0342]
8063
[Rint=0.0137]
6423
Table 2
,
Selected bond distances (A) and angles (°)
Refinement method Full-matrix L.S. on F2 Full-matrix L.S.
on F2
Molecule 3
RuꢀCt(1)
RuꢀP
RuꢀCl(1)
RuꢀCl(2)
PꢀC(11)
1.71
TiꢀCt(2)
TiꢀCt(3)
TiꢀCl(3)
TiꢀCl(4)
2.07
2.06
2.366(2)
2.329(2)
Data/restraints/param7316/0/466
eters
R for IRCGT
R for IRC
8063/6/380
2.3701(13)
2.4208(13)
2.4037(13)
1.834(5)
R1a=0.0435,
wR2b=0.108
R1 a=0.1086,
wR2b=0.129
1.036
R1a=0.0408,
wR2b=0.1082
R1a=0.0632,
wR2b=0.1205
1.014
Ct(1)ꢀRuꢀP
Ct(1)ꢀRuꢀCl(1) 125.7
Ct(1)ꢀRuꢀCl(2) 125.3
PꢀRuꢀCl(1)
PꢀRuꢀCl(2)
Cl(1)ꢀRuꢀCl(2) 88.47(5)
129.0
Ct(2)ꢀTiꢀCt(3) 131.9
Ct(2)ꢀTiꢀCl(3) 106.0
Ct(2)ꢀTiꢀCl(4) 107.4
Ct(3)ꢀTiꢀCl(3) 105.3
Ct(3)ꢀTiꢀCl(4) 106.3
Goodness-of-fit c
Largest Dz
0.756 and −0.639
1.219 and −0.979
−3
,
(e A
)
88.94(4)
86.55(4)
a R1=ꢀ(ꢁFoꢁ−ꢁFcꢁ)/ꢀꢁFoꢁ.
Cl(3)ꢀTiꢀCl(4)
93.39(6)
b wR2=[ꢀw(Fo2−Fc2)2/ꢀ[w(Fo2)2]1/2
where
w=1/[|2(F2o)+
Molecule 4
RuꢀCt(1)
RuꢀP
RuꢀCl(1)
RuꢀCl(2)
PꢀC(11)
(0.069*P)2+1.98P] for 3 and w=1/[|2(F2o)+(0.0654*P)2+2.22P]
1.70
TiꢀCt(2)
TiꢀCt(3)
TiꢀCl(3)
TiꢀCl(4)
2.06
for 4 where P=(max(F2o,0)+2*Fc2)/3.
2.3504(8)
2.419(1)
2.422(1)
1.829(3)
2.07 (2.05) a
2.370(2)
2.324(2)
c Goodness-of-fit=[ꢀw(F2o−F2c)2/(No−Nv)]1/2
.
Ct(1)ꢀRuꢀP
Ct(1)ꢀRuꢀCl(1) 125.8
Ct(1)ꢀRuꢀCl(2) 126.7
PꢀRuꢀCl(1)
PꢀRuꢀCl(2)
Cl(1)ꢀRuꢀCl(2) 87.63(4)
129.3
Cl(4)ꢀTiꢀCl(3)
95.26(8)
Ct(2)ꢀTiꢀCt(3) 131.2 (133.7) a
Ct(2)ꢀTiꢀCl(3) 104.3
hexane. The solution was then placed in a freezer
(−20°C) overnight. The solvent was removed by
filtration and the red residue was dried under vaccuum
(75% yield).
87.93(3)
86.98(3)
Ct(2)ꢀTiꢀCl(4) 106.2
Ct(3)ꢀTiꢀCl(3) 109.3 (103.2) a
Ct(3)ꢀTiꢀCl(4) 104.9 (107.6) a
31P{1H}-NMR (81.004 MHz, CDCl3) l −16.45 (s,
1
a Distance and angle values in brackets reference to the second
centroid of the desordered cyclopentadienyl ring.
PPh2). H-NMR (200.135 MHz, CDCl3) l 6.46 (s, 5H,
Cp), 6.58–6.66 (m, 4H, CpPPh2), 7.32–7.42 (m, 10H,

P. Le Gendre et al. / Journal of Organometallic Chemistry 605 (2000) 151–156
155
J=7.9 Hz), 2.96 (dt, 2H, CH2, J=10.0, J=7.9 Hz),
4.5. Complex 4
6.25–6.30 (m, 8H, Cp), 7.28–7.41 (m, 20H, Ph). Anal.
Calc. for C38H36Cl2P2Ti (673.4364): C, 67.77; H, 5.39.
Found: C, 67.01; H, 5.1%. The relatively low percent-
age of carbon can be attributed to the presence of LiCl.
Under the above experimental conditions, 90% of 4
was isolated as a brick powder, 31P{1H}-NMR (81.004
MHz, CDCl3) l 21.28 (s, PPh2). 1H-NMR (200.135
MHz, CDCl3) l 0.82 (d, 6H, isopropyl CH3, J=6,8
Hz), 1.89 (s, 3H, CH3 p-cymene), 2.35–2.60 (m, 3H,
CH2+CH isopropyl), 2.68–2.82 (m, 2H, CH2), 5.08 (d,
2H, ꢁCH p-cymene, J=6.2 Hz), 5.27 (d, 2H, ꢁCH
p-cymene, J=6.2 Hz), 6.18–6.21 (m, 2H, Cp), 6.31–
6.34 (m, 2H, Cp), 6.48 (s, 5H, Cp), 7.43–7.50 (m, 6H,
m,p-Ph), 7.81–7.91 (m, 4H, o-Ph). Anal. Calc. for
C34H37Cl4PRuTi (767.4023): C, 53.22; H, 4.86. Found:
C, 52.88; H, 4.96%.
4.4. Complex 3
A 25 ml Schlenk flask was charged under argon with
1 (0.4 g, 0.92 mmol), [(p-cymene)RuCl2]2 (0.28 g, 0.46
mmol) and degassed benzene. The mixture was stirred
at r.t. for 4 h during which time a brick precipitate
slowly formed. The solvent was removed by filtration
and the red residue was dried under vaccuum (85%
yield). 31P{1H}-NMR (81.004 MHz, CDCl3) l 15.07 (s,
4.5.1. X-ray analysis of 4
1
PPh2). H-NMR (200.135 MHz, CDCl3) l 1.04 (d, 6H,
Crystals for the X-ray structure analysis were ob-
tained by layering toluene onto a saturated chloroform
solution of 4 at r.t. A red crystal (0.30×0.30×0.22
mm3) was mounted on an Enraf–Nonius CAD4 dif-
isopropyl CH3, J=7.0 Hz), 1.69 (s, 3H, CH3 p-
cymene), 2.45 (hept, 1H, CH isopropyl, J=7.0 Hz),
5.13 (s apparent, 4H, ꢁCH p-cymene), 6.10 (s, 5H, Cp),
6.28–6.32 (m, 2H, Cp), 7.45–7.52 (m, 8H, m,p-Ph+
Cp), 7.84–7.94 (m, 4H, o-Ph). Anal. Calc. for
C32H33Cl4PRuTi (739.3487): C, 51.98; H, 4.50. Found:
C, 52.22; H, 4.58%.
fractometer. A total of 8511 reflections (8063 unique)
−1
,
were collected up to sin(q)/u=0.62 A
at r.t. The
data were corrected for Lorentz and polarization effects
[11] and for absorption (psi-scan method) [12]. No
decay was observed. The structure was solved via a
Patterson search program [13] and refined (space group
(
4.4.1. X-ray analysis of 3
P1) with full-matrix least squares methods based on
Crystals suitable for the X-ray structure analysis were
obtained by layering n-hexane onto a saturated chloro-
form solution of 3 at r.t. A dark red crystal (0.36×
0.28×0.25 mm3) was mounted in a capillary with the
mother liquor on an Enraf–Nonius CAD4 diffractome-
ꢁF2ꢁ. Except the carbon atoms of the toluene solvate
molecule (see below) all non-hydrogen atoms were
refined with anisotropic thermal parameters. The
methyl hydrogen atoms of the disordered toluene sol-
vate molecule were not included in the model while the
others were included in their calculated positions and
refined with a riding model. The terminal cyclopentadi-
enyl ring of the complex is desordered and occupies two
positions with refined occupation factors m1=0.53 and
m2=0.47. The rings are rotated with respect to each
ter. A total of 7675 reflections (7316 unique) were
−1
,
collected up to sin(q)/u=0.59 A
at r.t. The data
were corrected for Lorentz and polarization effects [11]
and for absorption (psi-scan method) [12]. A 65% decay
was linearly corrected. The structure was solved via a
Patterson search program [13] and refined (space group
,
other and their centroids are shifted by 0.22 A. The
(
P1) with full-matrix least squares methods based on
toluene solvate molecule is also desordered over two
positions and the refinement led to the occupations
factors m1=0.56 and m2=0.44. The carbon atoms of
the solvate were left isotropic and only two thermal
parameters were refined: one for the phenyl carbon
atoms and one for the methyl groups. The finals agree-
ment indices are wR2=0.121 for all data and R1=
0.0408 for 6423 intensities with I\2|(I). Final
difference electron density: Dz=1.219 (close to Cl(3))
ꢁF2ꢁ. Except for one carbon atom of a disordered sol-
vate molecule (see below) all non-hydrogen atoms were
refined with anisotropic thermal parameters. Hydrogen
atoms were included in their calculated positions and
refined with a riding model. The asymmetric unit con-
tains one molecule of the complex, two chloroform
molecules and 1/2 hexane molecule located on an inver-
sion center. One of the chloroform molecule is disor-
dered and occupies two positions with occupation
factors m1=0.68 and m2=0.32. Two chlorine atoms
are shared by the two molecules and then refined with
an occupation factor m=1. The carbon atom with the
smaller multiplicity was refined isotropically. The finals
agreement indices are wR2=0.129 for all data and
R1=0.0435 for 4886 intensities with I\2|(I). Final
difference electron density: Dz=0.756 and −0.639 e
and −0.979 e A−3. Crystal data are reported in Table
1.
,
4.6. Complex 6
Metallodiphosphine 5 (0.48 g, 0.75 mmol), and 0.46 g
(0.75 mmol) of [(p-cymene)RuCl2]2 were dissolved un-
der an inert atmosphere of argon in degassed CH2Cl2.
After stirring for 4 h, the solvent was evaporated and
−3. Crystal data are reported in Table 1.
,
A

156
P. Le Gendre et al. / Journal of Organometallic Chemistry 605 (2000) 151–156
Bergman, J. Am. Chem. Soc. 115 (1993) 2743. (d) A.M. Trze-
ciak, J.J. Ziolkowski, R. Choukroun, J. Mol. Catal. 110 (1996)
135.
the resulting red solid was purified by recrystallisation
from chloroform/hexane (60% yield).31P{1H}-NMR
(81,004 MHz, CDCl3) l 21.60 (s, PPh2). 1H-NMR
(200.135 MHz, CDCl3) l 0.80 (d, 12H, isopropyl CH3,
J=7.1 Hz), 1.87 (s, 6H, CH3 p-cymene), 2.30–2.47 (m,
4H, CH2), 2.51 (hept, 2H, CH isopropyl, J=7.1 Hz),
2.63–2.84 (m, 4H, CH2), 5.00 (d, 4H, ꢁCH p-cymene,
J=5.9 Hz), 5.24 (d, 4H, ꢁCH p-cymene, J=5.9 Hz),
5.99–6.02 (m, 4H, Cp), 6.16–6.19 (m, 4H, Cp), 7.43–
7.47 (m, 12H, m,p-Ph), 7.80–7.92 (m, 8H, o-Ph). Anal.
Calc. for C58H64Cl6P2Ru2Ti (1285.8296): C, 54.18; H,
5.02. Found: C, 53.74; H, 5.16%.
[3] (a) D.W. Stephan, Coord. Chem. Rev. 95 (1989) 41. (b) R.T.
Baker, W.C. Fultz, T.B. Morder, I.D. Williams, Organometallics
9 (1990) 2357. (c) R.M. Bullock, C.P. Casey, Acc. Chem. Res. 20
(1987) 167. (d) S.C. Yang, C.W. Hung, Synthesis 10 (1999) 1747.
(e) G. Poli, G. Giambastiani, A. Mordini, J. Org. Chem. 64
(1999) 2962.
[4] (a) W. Kaminsky, J. Chem. Soc. Dalton Trans. (1998) 1413. (b)
P.C. Mohring, N.J. Coville, J. Organomet. Chem. 479 (1994). (c)
P. Jutzi, T. Redeker, B. Neumann, H.G. Stammler,
Organometallics 15 (1996) 4153.
[5] (a) F. Simal, D. Jan, A. Demonceau, A.F. Noels, Tetrahedron
Lett. 40 (1999) 1653. (b) M. Kitamura, M. Tokunaga, R. Noy-
ori, J. Org. Chem. 57 (1992) 4053. (c) A. Fu¨rstner, M. Picquet,
C. Bruneau, P.H. Dixneuf, J. Chem. Soc. Chem. Commun.
(1998) 1351.
5. Supplementary material
[6] (a) J.C. Leblanc, C. Mo¨ıse, A. Maisonnat, R. Poilblanc, C.
Charrier, F. Mathey, J. Organometal. Chem. 231 (1982) C43. (b)
J. Szymoniak, M.M. Kubicki, J. Besanc¸on, C. Mo¨ıse, Inorg.
Chim. Acta 180 (1991) 153. (c) X.D. He, A. Maisonnat, F.
Dahan, R. Poilblanc, Organometallics 8 (1989) 2618. (d) E.
Delgado, J. Fornies, E. Hernandez, E. Lalinde, N. Mansilla,
M.T. Moreno, J. Organomet. Chem. 494 (1995) 261. (e) T.W.
Graham, A. Llamazares, R. McDonald, M. Cowie,
Organometallics 18 (1999) 3490. (f) T.W. Graham, A. Lla-
mazares, R. McDonald, M. Cowie, Organometallics 18 (1999)
3502.
[7] S. Serron, S.P. Nohan, Organometallics 14 (1995) 4611.
[8] C.K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National
Laboratory, Oak Ridge, TN, (1976).
[9] (a) J.F. Mai,Y. Yamamoto, J. Organomet. Chem. 560 (1998)
223. (b) J.F. Mai, Y. Yamamoto, J. Organomet. Chem. 545
(1997) 577
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC no. 140519 for the compounds 3
and CCDC no. 140520 for the compounds 4. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.aac.uk or www: http://www.ccdc.cam.ac.uk).
References
[1] Selected reports on heterobimetallic complexes: (a) W.J. Sartain,
J.P. Selegue, J. Am. Chem. Soc. 107 (1985) 5818. (b) G.S.
Graham, D.W. Stephan, Organometallics 6 (1987) 2169. (c) W.J.
Sartain, J.P. Selegue, Organometallics 8 (1989) 2153. (d) C.P.
Casey, R.F. Jordan, A.L. Rheingold, J. Am. Chem. Soc. 105
(1983) 665. (e) C. Bianchini, A.J. Meli, J. Am. Chem. Soc. 106
(1984) 2698.
[2] (a) L. Gelmini, D.W. Stephan, Organometallics 5 (1986) 67. (b)
R. Choukroun, D. Gervais, P. Kalck, F. Senocq, J. Organomet.
Chem. 335 (1987) C9. (c) M.J. Hostetler, M.D. Butts, R.G.
[10] (a) F. Mathey, J.P. Lampin, Tetrahedron 31 (1975) 2685. (b) T.
Kauffmann, M. Bisling, J.H. Teuben, R. Konig, Angew. Chem.
Int. Ed. Engl. 19 (1980) 328.
[11] K. Harms, University of Marburg, (1996).
[12] (a) A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr.
Sect. A 24 (1968) 351. (b) A.L. Spek, Acta Crystallogr. Sect. A:
Found. Crystallogr. 46 (1990) C34.
[13] C.K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National
Laboratory, Oak Ridge, TN, (1976).
.