Reactivity of the 1-azavinylidene cluster [Ru3(μ-H)(μ-N=CPh2)(CO)10] with hydrogen, tertiary silanes and tertiary stannanes

Article abstract of DOI:10.1016/S0022-328X(98)00716-5

The reactivity of the 1-azavinylidene cluster [Ru₃(μ-H)(μ-N=CPh₂)(CO)₁₀] (1) with hydrogen, tertiary silanes and tertiary stannanes has been investigated. The reaction of 1 with hydrogen (1 atm, 110°C) gives [Ru₄

Full text of DOI:10.1016/S0022-328X(98)00716-5

Journal of Organometallic Chemistry 564 (1998) 201–207
Reactivity of the 1-azavinylidene cluster [Ru3(v-H)(v-NꢀCPh2)(CO)10]
with hydrogen, tertiary silanes and tertiary stannanes
Claudette Bois a, Javier A. Cabeza b,*, R. Jesu´s Franco b, V´ıctor Riera b, Enrique Saborit b
a Laboratoire de Chimie des Me´taux de Transition, Uni6ersite´ Pierre et Marie Curie, URA-CNRS 419, 4 Place Jussieu,
F-75252 Paris Cedex, France
b Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto de Qu´ımica Organometa´lica ‘Enrique Moles’, Uni6ersidad de O6iedo-CSIC,
E-33071 O6iedo, Spain
Received 19 March 1998; received in revised form 11 May 1998
Abstract
The reactivity of the 1-azavinylidene cluster [Ru3(v-H)(v-NꢀCPh2)(CO)10] (1) with hydrogen, tertiary silanes and tertiary
stannanes has been investigated. The reaction of 1 with hydrogen (1 atm, 110°C) gives [Ru4(v-H)4(CO)12] and H2NCHPh2 as
end-products, proceeding via the imido and amido intermediates [Ru3(v-H)2(v3-NCHPh2)(CO)9] (2) and [Ru3(v-H)(v-
HNCHPh2)(CO)10] (3), respectively. Although no reaction is observed between compound 1 and tertiary organosilanes at 110°C,
1 reacts readily with tertiary organostannanes to give [Ru3(v-H)2(v-NꢀCPh2)(SnR3)(CO)9] (4: R=Ph; 5: R=Bu). 1H-NMR
spectroscopy and the X-ray structure of the triphenylstannyl derivative 4 demonstrate that the addition of the stannane reagents
to 1 takes place on the cluster metal framework. No transfer of the stannyl group from the metal to the azavinylidene ligand is
observed at 110°C. This is in contrast with the results obtained in the hydrogenation of 1, where reduction of the azavinylidene
ligand is observed under comparable reaction conditions. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Cluster; Azavinylidene; Hydrogenation; Tertiary stannane; X-ray structure
1. Introduction
On the other hand, all the other previous examples
of transition metal carbonyl cluster compounds con-
taining 1-azavinylidene ligands are of the type [M3(v-
H)(v-NꢀCHR)(CO)10] and have been prepared in low
yields by hydrogenation of nitriles on iron [4], ruthe-
nium [5–9] and osmium [10–12] carbonyl clusters,
but the low efficiency of these syntheses has pre-
vented a subsequent development of their derivative
chemistry.
We have recently reported a high-yield synthesis of
the trinuclear 1-azavinylidene complex [Ru3(v-H)(v-
NꢀCPh2)(CO)10] (1), starting from [Ru3(CO)12] and
benzophenone imine [1]. Reactivity studies on com-
pound 1 have shown that: (a) it easily undergoes substi-
tution of carbonyl ligands by phosphine ligands [1]; (b)
it reacts with diphenylacetylene experiencing an unusual
insertion of the alkyne into a metal–nitrogen bond [2];
(c) its carbonyl-substituted phosphine derivatives un-
dergo protonation at the metal atoms but not at the
azavinylidene fragment [3]; and (d) the azavinylidene
ligand can also coordinate to three metal atoms in a
face-capping mode [1].
We now report the reactivity of compound 1 with
hydrogen. We undertook this study having in mind
that
compounds
of
the
type
[Ru3(v-H)(v-
NꢀCHR)(CO)10] are intermediates in the hydrogena-
tion of nitriles to amines promoted by [M3(CO)12]
(M=Fe [4,13,14], Ru [7], Os [12]) and that, therefore,
a study of the reactivity of the readily available com-
pound 1 with hydrogen would shed more light on the
mechanism of this hydrogenation reaction.
* Corresponding author. Tel.: +34 98 5103501: fax:+34 98
5103446; e-mail: jac@sauron.quimica.uniovi.es
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00716-5

202
C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
Scheme 1
In addition, the reactivity of compound 1 with tri-
ertheless, they could be identified by analysing the
1H-NMR spectra the mixtures obtained at various reac-
tion times (Table 1). Thus, excluding the resonances
due to the phenyl groups, compound 2 is characterized
by two singlet resonances in a 2:1 ratio, while com-
pound 3 is characterized by three resonances, in a 1:1:1
integral ratio, whose chemical shifts and multiplicities
unequivocally allow their assignment (Table 1). Confir-
ming our assignment, the ratio of the resonances be-
longing to the same compound is maintained constant
organosilanes and triorganostannanes is also reported
and compared with that observed with hydrogen. Hy-
drosilylated and hydrostannanted products are also of
interest [15,16], and triorganosilanes and triorganostan-
nanes often react with unsaturated organic molecules
[15,16] and transition metal clusters [17] in a similar
way as hydrogen.
2. Results and discussion
Table 1
Selected 1H-NMR data (l ppm)a
2.1. Hydrogenation reactions
Compound v-H
Other
Treatment of the 1-azavinylidene cluster [Ru3(v-
H)(v-NꢀCPh2)(CO)10] (1) with hydrogen (1 atm) in
toluene at reflux temperature gave [Ru4(v-H)4(CO)12]
and H2NCHPh2 as end-products. The reaction required
at least 6 h to be completed. The imido and amido
derivatives [Ru3(v-H)2(v3-NCHPh2)(CO)9] (2) and
2b
3b
−17.16 (s, 2H)
5.64 (s, 1H), CHPh2
−13.73 (d, 1H) [1.1] 5.81 (dd, 1H) [11.6, 1.1], NH
3.93 (d, 1H) [11.6], CHPh2
4
5
−12.06 (sc, 1H),
−13.43 (s, 1H)
7.5–6.5 (m, 25H), 5Ph
[Ru3(v-H)(v-HNCHPh2)(CO)10]
(3),
respectively
−12.41 (sd, 1H),
−12.69 (s, 1H)
7.4–7.1 (m, 10H), 2Ph
1.6–0.8 (m, 27H), 3Bu
(Scheme 1), were identified in the reacting solution with
the help of NMR spectroscopy at intermediate reaction
times.
Compounds 2 and 3 were separated by chromato-
graphic means from the other components of the reac-
tion mixtures, but all attempts to separate these
complexes from each other resulted unsuccessful. Nev-
a Spectra were recorded in CDCl3; multiplicities are given in paren-
theses; coupling constants (Hz) are given in square brackets.
b The resonances of the phenyl groups of 2 cannot be distinguished
from those of 3.
c With tin satellites, J(117Sn– H) A ca. J( Sn– H) A 39 Hz.
1
119
1
˚
˚
˚
˚
d With tin satellites, J(117Sn- H) A ca. J( Sn– H) A 37 Hz.
1
119
1

C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
203
Fig. 1. Hydride region of the 1H-NMR spectra of samples obtained at different reaction times during the hydrogenation (1 atm) of compound
1 in refluxing toluene. The scale and peak assignments are only given in the central spectrum but are common to the five spectra.
for several hours. A subsequent reaction of [Ru3(v-
H)(v3-NꢀCPh2)(CO)9] with hydrogen would lead to
compound 2 (in several steps).
in the spectra of samples obtained after different reac-
tion times, where the ratio of 2 and 3 is not maintained.
Furthermore, the chemical shifts reported for the hy-
dride ligands of the X-ray structurally characterized
imido and amido compounds [Ru3(v-H)2(v3-NCH2-p-
C6H4OMe)(CO)9] (−17.17 ppm) [6] and [Ru3(v-H)(v-
HNCH2Ph)(CO)10] (−13.52 ppm) [18] are comparable
to those we report here for 2 and 3, respectively.
Monitoring the reaction of compound 1 with hydro-
gen by 1H-NMR spectroscopy (Fig. 1) revealed that: (a)
complex 2 is the first intermediate cluster formed at the
expenses of 1 (major product after 45 min); (b) the
amount of the amido complex 3 increases very slowly
during the first 90 min; (c) after 90 min, the amounts of
both 2 and 3 slowly decrease until they completely
disappear; and (d) the amount of [Ru4(v-H)4(CO)12]
continuously increases as the reaction progresses.
As 2 seems to be formed prior than 3 in the reaction
and as the hydrogenation of the CꢀN moiety of 1
requires its y-coordination to a metal atom in order to
allow the transfer of a hydride from the metal to the
carbon atom, we propose the existence of an elusive
In order to establish the connection between 2 and 3
in the hydrogenation reaction of 1, the thermolysis
under nitrogen of a mixture of these two compounds in
refluxing toluene was monitored by 1H-NMR spec-
troscopy. Interestingly, the amounts of both 2 and 3
decreased with time, while 1 and [Ru4(v-H)4(CO)12]
were progressively formed (Fig. 2). An IR spectrum
and a spot TLC analysis of the resulting solution also
showed the presence of [Ru3(CO)12] in the reaction
mixture. These data, coupled to the fact that both 2 and
3 give [Ru4(v-H)4(CO)12] under hydrogen (Fig. 1), sug-
gest that both compounds are connected through a
common, very unstable, intermediate which is a com-
mon product of their thermolysis, which reacts with
hydrogen (in several steps) to give [Ru4(v-H)4(CO)12],
(not
detected)
intermediate,
[Ru3(v-H)(v3-
NꢀCPh2)(CO)9], which contains the azavinylidene lig-
and in a face-capping mode (Scheme 1). Such a
coordination mode for an azavinylidene ligand has
precedents in iron [4] and ruthenium [1] carbonyl clus-
ter chemistry. The equilibrium that leads from 1 to
[Ru3(v-H)(v3-NꢀCPh2)(CO)9] should be very displaced
to the left, since the latter was not detected when
complex 1 was stirred in toluene at reflux temperaure
Fig. 2. Hydride region of the 1H-NMR spectrum of a sample
obtained by thermolysis under nitrogen of a ca. 1:1 mixture of 2 and
3 in refluxing toluene for 2.5 h.

204
C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
ported as oils [17,19–21]. The IR spectra of 4 and 5
are very similar, suggesting an analogous structure
for both compounds, and show the w(CO) absorp-
tions shifted to higher wavenumbers than those of
complex 1 [1], as expected for a higher formal oxida-
tion state of the metal atoms. Their 1H-NMR spec-
tra (Table 1) clearly indicate the incorporation of a
new hydride and one SnR3 group to the original
complex. However, with all these spectroscopic data
it was not possible to precisely locate the position of
the corresponding SnR3 group on the clusters and,
thus, an X-ray diffraction study was carried out.
Fig. 3 represents the X-ray molecular structure of
compound 4. Selected bond lengths and angles are
given in Table 2. The cluster consists on a triangular
array of ruthenium atoms with one of the edges be-
ing spanned by the nitrogen atom of the 1-azavinyli-
dene ligand, which occupies two axial coordination
sites. That edge and one of the two remaining edges
are also bridged by hydride ligands. Although the lo-
cation of hydrides by X-ray methods has always to
be considered cautiously, in this case the X-ray data
fit consistently with the NMR data. The SnPh3
group is coordinated, in an equatorial position, to
the ruthenium atom attached to the two hydrides.
The ligand shell of the cluster is completed by nine
CO ligands. Overall, this structure can be compared
to that of the cluster [Ru3(v-H)2(v3-ampy)
(SiEt3)(CO)8] (Hampy=2-amino-6-methylpyridine), in
which the ampy ligand occupies three axial coordina-
tion sites [22], although it differs in that the SnPh3
group of 4 is cis to the hydride which spans the
same edge as the bridging ligand, whereas the SiEt3
group of the ampy complex is trans to the analogous
hydride ligand.
All attempts to efficiently promote the transfer of
the stannyl group of complex 4 from the metal to
the azavinylidene ligand (refluxing in toluene, treat-
ment with carbon monoxide or with triphenylphos-
phine in refluxing toluene) were unsuccessful, since
they failed to give a tractable product. Therefore, no
products derived from hydrostannated 1-azavinyli-
dene could be prepared and this contrasts with the
results commented above on the reaction of com-
pound 1 with hydrogen, where the hydrogenation of
the 1-azavinylidene ligand is achieved. However, the
synthesis and structural characterization of com-
pounds 4 and 5 may shed some more light on the
mechanism of the reaction of compound 1 with hy-
drogen. In fact, a compound which would result
from the formal substitution of the SnR3 group in 4
or 5 by a hydrogen atom would well be one of the
missing intermediates that link the complex [Ru3(v-
H)(v-NꢀCPh2)(CO)9] with cluster 2 in Scheme 1.
Scheme 2.
and which decomposes on heating in the absence of
hydrogen to give mixture of compound 1,
a
[Ru3(CO)12] and [Ru4(v-H)4(CO)12]. The unsaturated
46-electron derivative [Ru3(v-H)(v-HNCHPh2)(CO)9],
which would arise under thermal conditions from the
hydrogen transfer of a hydride from the metal to the
nitrogen atom of 2 and from the release of a CO
ligand from 3, would be a reasonable proposal for
such an unstable intermediate. This would also ac-
count for the small amount of complex 3 formed
during the hydrogenation reaction, since the forma-
tion of 3 from the unsaturated intermediate [Ru3(v-
H)(v-HNCHPh2)(CO)9] requires carbon monoxide
and only a small amount of the latter should be
available in solution.
All this data, coupled to previous data on related
systems, have allowed us to propose Scheme 1 as a
mechanism for the hydrogenation of compound 1.
As commented in the introductory section, 1-aza-
vinylidene
derivatives
of
type
[M3(v-H)(v-
NꢀCHR)(CO)10] (M=Fe, Ru, Os) are intermediates
in the hydrogenation of nitriles to amines promoted
by the corresponding carbonyl metal cluster; there-
fore, the mechanism shown in Scheme 1 also repre-
sents a mechanism for that reaction, being the most
complete proposal reported so far [12,14].
2.2. Reactions with tertiary silanes and tertiary
stannanes
No reaction was observed between compound 1
and an excess of triethylsilane or triphenylsilane
(toluene, reflux temperature, 1 h). However, under
milder reaction conditions (1,2-dichloroetane, reflux
temperature, 15 min), compound
triphenylstannane and tributylstannane to give the
stannyl derivatives [Ru3(v-H)2(v-NꢀCPh2)(SnR3)-
(CO)9] (4: R=Ph; 5: R=Bu) in high yields (Scheme
2). Compound 4 was obtained as a crystalline yellow
solid, but compound 5 was obtained as a tan oil
which could not be crystallized. Other tributylstannyl
derivatives of triruthenium clusters have also been re-
1 reacted with

C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
205
3. Experimental details
h, while a hydrogen flow was continuously bubbled
through the solution. The solvent was removed under
reduced pressure and the residue was separated by
preparative TLC on silica gel. Three yellow bands were
eluted with hexane as eluant and were extracted from
the support with dichloromethane. The corresponding
solutions were evaporated to dryness to give yellow
solids. The first and second bands contained [Ru4(v-
H)4(CO)12] and compound 1, respectively (identified by
3.1. General data
Solvents were dried over sodium diphenyl ketyl (di-
ethyl ether, hydrocarbons) or CaH2 (dichloromethane,
1,2-dichloroethane) and distilled under nitrogen prior
to use. The reactions were carried out under hydrogen
or nitrogen, as necessary, using Schlenk-vacuum line
techniques, and were routinely monitored by solution
IR spectroscopy (carbonyl stretching region). Com-
pound 1 was prepared as described previously [1]. Hy-
drogen (99.995%) was obtained from Air Liquide. All
the other reagents and chromatographic supports were
purchased from Aldrich and were used as received.
Infrared spectra were recorded on a Perkin-Elmer FT
1720-X spectrophotometer, using 0.1 mm CaF2 cells.
1H-NMR spectra were run at 20°C with Bruker AC-200
and AC-300 instruments, using SiMe4 as internal stan-
dard (l=0 ppm). Microanalyses were obtained from
the University of Oviedo Analytical Service.
1
their IR and H-NMR spectra). The third band was
identified as a mixture of compounds 2 and 3, in ca. 1:1
1
ratio, by H-NMR spectroscopy. All attempts to sepa-
rate these compounds by chromatographic means were
unsuccessful. Longer reaction times resulted in higher
yields of [Ru4(v-H)4(CO)12] and in lower yields of the
mixture 2+3. [Ru4(v-H)4(CO)12] was the only complex
obtained after 6 h of reaction, while the presence of
H2NCHPh2 in the solution was confirmed by GC-MS.
1
3.3. H-NMR monitoring of the reaction of complex 1
with hydrogen
3.2. Reaction of complex 1 with hydrogen
A solution of compound 1 (300 mg, 0.390 mmol) in
toluene (40 ml) was stirred at reflux temperature while
a hydrogen flow was continuously bubbled through the
solution. At different reaction times, 5 ml aliquots of
A solution of compound 1 (300 mg, 0.390 mmol) in
toluene (20 ml) was stirred at reflux temperature for 1.5
Fig. 3. Molecular structure of compound 4.

206
C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
Table 2
1.15. IR (CH2ClCH2Cl): 2115 (s), 2072 (s), 2050 (sh),
˚
Selected bond lengths (A) and angles (°) in 4·(Et2O)0.5
2039 (vs), 2019 (sh), 1963 (m) cm−1
.
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–Sn(1)
Ru(1)–N(1)
Ru(2)–N(1)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(2)–C(3)
Ru(2)–C(4)
Ru(2)–C(5)
Ru(3)–C(6)
Ru(3)–C(7)
Ru(3)–C(8)
2.7942(7)
3.0888(7)
2.8654(7)
2.6382(6)
2.076(4)
2.096(4)
1.887(7)
1.863(6)
1.914(7)
1.897(7)
1.926(7)
1.930(8)
1.944(8)
1.937(8)
Ru(3)–C(9)
O(1)–C(1)
O(2)–C(2)
O(3)–C(3)
O(4)–C(4)
O(5)–C(5)
O(6)–C(6)
O(7)–C(7)
O(8)–C(8)
O(9)–C(9)
N(1)–C(20)
C(10)–C(20)
C(10)–C(30)
1.887(7)
1.129(7)
1.148(7)
1.128(7)
1.140(7)
1.134(8)
1.128(9)
1.132(9)
1.133(8)
1.140(8)
1.272(7)
1.484(8)
1.511(8)
3.6. Preparation of
[Ru3(v-H)2(v-NꢀCPh2)(SnBu3)(CO)9] (5)
A solution of compound 1 (100 mg, 0.130 mmol)
and HSnBu3 (80 ml, 0.261 mmol) in 1,2-
dichloroethane (10 ml) was stirred at reflux tempera-
ture for 20 min. The colour changed from orange to
red. The solution was concentrated under reduced
pressure to ca. 1.5 ml and then it was applied to a
column of neutral alumina (2×10 cm, activity I,
packed in hexane). A hexane/dichloromethane (10:1)
mixture eluted a red band which afforded compound
Ru(1)–Ru(2)–Ru(3) 66.14(2)
Ru(1)–Ru(3)–Ru(2) 55.82(4)
Ru(2)–Ru(1)–Ru(3) 58.04(2)
Ru(2)–Ru(1)–Sn(1) 98.29(2)
Ru(3)–Ru(1)–Sn(1) 154.46(2)
Ru(2)–Ru(1)–N(1) 48.3(1)
Ru(1)–Ru(2)–N(1) 47.7(1)
Ru(1)–N(1)–Ru(2) 84.1(2)
Ru(2)–Ru(3)–C(6) 89.9(2)
Ru(3)–Ru(2)–N(1) 84.2(1)
5
as
(CH2ClCH2Cl): 2112 (s), 2065 (s), 2050 (sh), 2035
(vs), 2009 (s), 1951 (m) cm−1
a
tan oil after solvent removal. IR
Ru(1)–N(1)-C(10)
142.6(4)
.
Ru(2)–N(1)–C(10) 133.2(4)
N(1)–C(10)–C(20) 124.5(5)
N(1)–C(10)–C(30) 121.3(5)
3.7. Crystal structure determination of 4 ·(Et2O)0.5
A yellow crystal, selected from a batch obtained at
the solution were syringed out. The solvent of each
aliquot was removed under reduced pressure and the
residue was dissolved in CDCl3 (1 ml) and was
−20°C by slow diffusion of hexane into a diethyl-
Table 3
1
Crystallographic and refinement data for 4·(Et2O)0.5
analysed by H-NMR spectroscopy (Fig. 1).
Formula
C40H27NO9Ru3Sn·(Et2O)0.5
3.4. Thermolysis of a mixture of compounds 2 and 3
Formula weight
Crystal system
Space group
1124.62
Monoclinic
P21/n
A solution containing a ca. 1:1 mixture of com-
pounds 2 and 3 (20 mg) in toluene (10 ml) was
stirred under nitrogen at reflux temperature for 2.5 h
and then concentrated to ca. 2 ml. A spot TLC anal-
ysis of this solution indicated the presence of
[Ru3(CO)12], [Ru4(v-H)4(CO)12], 1 and 2 or/and 3.
The presence of H2NCHPh2 was confirmed by GC-
MS. The solvent was removed under reduced pressure
and the residue was dissolved in CDCl3 and was
Unit cell dimensions
˚
a (A)
10.274(2)
21.283(6)
19.497(4)
95.90(2)
4241(3)
4
1736
1.76
˚
b (A)
˚
c (A)
i (°)
3
˚
V (A )
Z
F(000)
Dcalc. (g cm−3
)
v (mm−1
)
16.66
0.30×0.20×0.20
Mo–Kh, 0.71073
1
analysed by H-NMR spectroscopy (Fig. 2).
Crystal size (mm)
Radiation, u (A)
˚
Diffractometer
Monochromator
Temperature (K)
Scan method
Scan range (°)
q limits (°)
h, k, l ranges
Reflections collected
Independent reflections
Enraf-Nonius CAD4
Graphite
293(2)
v−2q
0.8+0.345 tgq
1–25
(−12, 0, 0) to (12, 25, 23)
7921
7437
0.047
5171
508
3.5. Preparation of
[Ru3(v-H)2(v-NꢀCPh2)(SnPh3)(CO)9] (4)
A solution of compound 1 (50 mg, 0.065 mmol)
and HSnPh3 (46 mg, 0.130 mmol) in 1,2-
dichloroethane (10 ml) was stirred at reflux tempera-
ture for 20 min. The colour changed from orange to
yellow. The solution was concentrated under reduced
pressure to ca. 1.5 ml and then it was applied to a
column of neutral alumina (2×7 cm, activity I,
packed in hexane) in order to remove the excess of
stannane reagent. A hexane/dichloromethane (10:1)
mixture eluted a yellow band which afforded com-
pound 4 as a yellow solid after solvent removal (65
mg, 72%). Anal. Calc. for C40H27NO9Ru3Sn: C,
44.17; H, 2.50; N, 1.28. Found: C, 44.51; H, 2.79; N,
R
int=ꢀ(I−BI\)/ꢀI
Reflections with F2o\3|(Fo2)
Parameters
Absorption coefficient
DIFABS (min=0.81, max=1.26)
0.030
0.032
0.87, −0.60
Ra
Rwb
−3
˚
Max, min Dz (e A
)
a R=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ.
b Rw=[ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/ꢀwF2o]1/2, unit weight.

C. Bois et al. / Journal of Organometallic Chemistry 564 (1998) 201–207
207
[4] M.A. Andrews, G. van Burskirk, C.B. Knobler, H.D. Kaesz, J.
Am. Chem. Soc. 101 (1979) 7245.
[5] P.M. Lausarot, M. Turini, G.A. Vaglio, M. Valle, A. Tiripic-
chio, M.T. Tiripicchio-Camellini, P. Gariboldi, J. Organomet.
Chem. 273 (1984) 239.
[6] P.M. Lausarot, L. Operti, G.A. Vaglio, M. Valle, A. Tiripicchio,
M.T. Tiripicchio-Camellini, P. Gariboldi, Inorg. Chim. Acta 122
(1986) 103.
[7] W. Bernhardt, H. Vahrenkamp, Angew. Chem. Int. Ed. Engl. 23
(1984) 381.
ether solution of complex 4, was used for the X-ray
diffraction study. A selection of crystal and refinement
data is given in Table 3. The space group P21/n was
determined from systematic absences. Two standard
reflections were monitored periodically, revealing no
intensity fluctuations. An empirical absorption correc-
tion (DIFABS) [23] and Lorentz and polarization cor-
rections were applied.
The structure was solved by direct methods and
successive Fourier maps. Computations were performed
using the CRYSTALS package [24]. Atomic form fac-
tors were taken from the literature [25]. Real and
imaginary parts of anomalous dispersion were taken
into account. A disordered diethylether molecule was
found on an inversion center, but it did not appear
clearly and was refined with constraints with an overall
isotropic thermal parameter. Almost all hydrogen
atoms were found on difference maps, but their posi-
tions were not refined, except those of the hydrides
H(1) and H(2) which were given individual isotropic
thermal parameters. Non-hydrogen atoms were an-
isotropicaly refined, except those of the solvent
molecule. Refinements were carried out in three blocks
by minimising the function [ꢀw(ꢁFoꢁ−ꢁFcꢁ)]. The struc-
ture plot was drawn with CAMERON [26]. Final
atomic coordinates have been deposited within the
Cambridge Crystallographic Data Centre.
[8] W. Bernhardt, C. von Schnering, H. Vahrenkamp, Angew.
Chem. Int. Ed. Engl. 25 (1986) 279.
[9] W. Bernhardt, H. Vahrenkamp, Z. Naturforsch B43 (1988) 643.
[10] R.D. Adams, D.A. Katahira, L.W. Yang, J. Organomet. Chem.
219 (1981) 85.
[11] R.D. Adams, D.A. Katahira, L.W. Yang, J. Organomet. Chem.
219 (1981) 241.
[12] J. Banford, Z. Dawoodi, K. Herick, M.J. Mays, J. Chem. Soc.
Chem. Commun. (1982) 554.
[13] M.A. Andrews, H.D. Kaesz, J. Am. Chem. Soc. 101 (1979) 7238.
[14] M.A. Andrews, H.D. Kaesz, J. Am. Chem. Soc. 101 (1979) 7255.
[15] For a review on catalytic hydrosilylation of organic substrates,
see: B. Marciniec (Ed.), Comprehensive Handbook on Hydrosi-
lylation, Pergamon, Oxford, UK, 1992.
[16] For examples of catalytic hydrostannation of organic substrates,
see: M.A. Esteruelas, F.J. Lahoz, M. Oliva´n, E. On˜ate, L.A.
Oro, Organometallics 14 (1995) 3486, and references therein.
[17] For examples of reactions of hydrosilanes and hydrostannanes
with ruthenium carbonyl clusters, see: J.A. Cabeza, R.J. Franco,
V. Riera, S. Garc´ıa-Granda, J.F. Van der Maelen, Organometal-
lics 14 (1995) 3342, and references therein.
[18] P.M. Lausarot, G.A. Vaglio, M. Valle, A. Tiripicchio, M.T.
Tiripicchio-Camellini, P. Gariboldi, J. Chem. Soc. Chem. Com-
mun. (1983) 1391.
[19] J.A. Cabeza, R.J. Franco, A. Llamazares, V. Riera, C. Bois, Y.
Jeaanin, Inorg. Chem. 32 (1993) 4640.
[20] J.A. Cabeza, R.J. Franco, V. Riera, Inorg. Chem. 33 (1994)
5952.
Acknowledgements
We are grateful to the Spanish DGES for financial
support (Project PB95-1042).
[21] J.A. Cabeza, S. Garc´ıa-Granda, A. Llamazares, V. Riera, J.F.
Van der Maelen, Organometallics 12 (1993) 157.
[22] J.A. Cabeza, A. Llamazares, V. Riera, S. Triki, L. Ouahab,
Organometallics 11 (1992) 3334.
[23] N. Walker, D. Stuart, Acta Crystallogr. A39 (1983) 158.
[24] J.R. Carruthers, D.J. Watkin, CRYSTALS, an Advanced Crys-
tallographic Computer Program, University of Oxford Chemical
Laboratory, Oxford, UK, 1985.
[25] International Tables for X-Ray Crystallography, vol. 4, Kynoch
Press, Birmingham, UK, 1974 (present distributor: Kluwer Aca-
demic Publishers, Dordrecht, The Netherlands).
References
[1] P.L. Andreu, J.A. Cabeza, I. del R´ıo, V. Riera, C. Bois,
Organometallics 15 (1996) 3004.
[2] J.A. Cabeza, I. del R´ıo, R.J. Franco, F. Grepioni, V. Riera,
Organometallics 16 (1997) 2763.
[3] J.A. Cabeza, I. del R´ıo, V. Riera, D. Ardura, J. Organomet.
Chem. 554 (1998) 117.
[26] L.J. Pearce, D.J. Watkin, CAMERON, University of Oxford
Chemical Laboratory, Oxford, UK, 1985.
.