A series of triisopropylstibine ruthenium and osmium complexes including the X-ray crystal structure of [RuCl2(CO)(SbiPr3)3] and [RuCl2(=C=C=CPh2)(CO)(SbiPr3)2]

Article abstract of DOI:10.1016/S0022-328X(98)00623-8

With [(p-cym)RuCl₂]₂ (1) as the starting material, the halfsandwich-type complexes [(p-cym)RuCl₂(SbiPr₃)] (2) and [(p-cym)RuCl(SbiPr₃)₂]PF₆ (3) were prepared. Treatment of RuCl₃·3H₂O in ethanol gave, after addition of SbiPr₃, the monocarbonyl compound [RuCl₂(CO)(SbiPr₃)₃] (4), which reacted with CO by ligand exchange to yield [RuCl₂(CO)₂(SbiPr₃)₂] (5). The reaction of RuCl₃·3H₂O in ethanol, in the presence of Na₂CO₃, afforded the chloro(hydrido) derivative [RuHCl(CO)(SbiPr₃)₃] (6). Analogously, using OsCl₃·3H₂O as the starting material, the chloro(hydrido)osmium complex [OsHCl(CO)(SbiPr₃)₃] (8) was prepared. The reactions of 8 with C₂H₄, C₂(CO₂Me)₂ and NaBH₄ led to the formation of compounds 9, 10 and 11, which all contain the Os(SbiPr₃)₂ unit as a building block. While treatment of 6 with C₂(CO₂Me)₂ yielded the substitution product [RuHCl(CO)(MeO₂CCCCO₂Me)(SbiPr₃)₂] (14), the corresponding reaction of 6 with HCCPh and HCCCPh₂OH afforded the alkynyl and allenylidene ruthenium(II) complexes [RuCl(CCPh)(CO)(SbiPr₃)₃] (16) and [RuCl₂(=C=C=CPh₂)(CO)(SbiPr₃)₂] (17), respectively. Compounds 4 and 17 were characterized by X-ray crystal structure analysis.

Full text of DOI:10.1016/S0022-328X(98)00623-8

Journal of Organometallic Chemistry 565 (1998) 231–241
A series of triisopropylstibine ruthenium and osmium complexes
including the X-ray crystal structure of [RuCl2(CO)(SbiPr3)3] and
[RuCl2(ꢀCꢀCꢀCPh2)(CO)(SbiPr3)2]1
H. Werner *, C. Gru¨nwald, P. Steinert, O. Gevert, J. Wolf
Institut fu¨r Anorganische Chemie der Uni6ersita¨t Wu¨rzburg, Am Hubland, D-97074 Wu¨rzburg, Germany
Received 1 January 1998
Abstract
With [(p-cym)RuCl2]2 (1) as the starting material, the halfsandwich-type complexes [(p-cym)RuCl2(SbiPr3)] (2) and [(p-
cym)RuCl(SbiPr3)2]PF6 (3) were prepared. Treatment of RuCl3 ·3H2O in ethanol gave, after addition of SbiPr3, the monocarbonyl
compound [RuCl2(CO)(SbiPr3)3] (4), which reacted with CO by ligand exchange to yield [RuCl2(CO)2(SbiPr3)2] (5). The reaction
of RuCl3 ·3H2O in ethanol, in the presence of Na2CO3, afforded the chloro(hydrido) derivative [RuHCl(CO)(SbiPr3)3] (6).
Analogously, using OsCl3 ·3H2O as the starting material, the chloro(hydrido)osmium complex [OsHCl(CO)(SbiPr3)3] (8) was
prepared. The reactions of 8 with C2H4, C2(CO2Me)2 and NaBH4 led to the formation of compounds 9, 10 and 11, which all
contain the Os(SbiPr3)2 unit as a building block. While treatment of 6 with C2(CO2Me)2 yielded the substitution product
[RuHCl(CO)(MeO2CCꢁCCO2Me)(SbiPr3)2] (14), the corresponding reaction of 6 with HCꢁCPh and HCꢁCCPh2OH afforded the
alkynyl and allenylidene ruthenium(II) complexes [RuCl(CꢁCPh)(CO)(SbiPr3)3] (16) and [RuCl2(ꢀCꢀCꢀCPh2)(CO)(SbiPr3)2] (17),
respectively. Compounds 4 and 17 were characterized by X-ray crystal structure analysis. © 1998 Elsevier Science S.A. All rights
reserved.
Keywords: Ruthenium; Osmium; Stibine complexes; Reactions with alkenes and alkynes
1. Introduction
m(II) derivatives [4]. When we attempted to obtain
[RuCl2(SbiPr3)3] or [RuCl2(SbiPr3)4] from the poly-
meric [RuCl2(C8H12)]n and SbiPr3 in the presence of H2,
we isolated the dihydrido(dihydrogen) complex
[RuH2(H2)(SbiPr3)3] in excellent yield [5]. This species
reacted with propene to give a bis(allyl)ruthenium(II),
After we discovered that low-valent rhodium [1] and
iridium [2] complexes with SbiPr3 as ligand are consid-
erably more reactive than their PiPr3 counterparts, we
became interested in preparing ruthenium(II) com-
pounds of the general composition [RuCl2(SbiPr3)n].
and with butadiene to afford
ene)ruthenium(0) derivative [5].
a
bis(butadi-
While
the
complexes
[RuCl2(SbPh3)4]
and
[RuCl2(SbMe2Ph)4] were known [3], there was no report
in the literature about related trialkylstibine rutheniu-
The work presented in this paper is not only an
extension of our recent investigations but reveals that
even RuCl3 ·3H2O as well as OsCl3 ·3H2O can be used
as starting materials for the synthesis of triisopropyl-
stibine ruthenium and osmium complexes. Moreover, it
illustrates that with Ru(SbiPr3)2 as a molecular building
block, an allenylidene unit: CꢀCꢀCPh2 can be generated
at ruthenium as the metal center also.
* Corresponding author. Tel.: +49 931 8885260; fax: +49 931
8884605.
1 Dedicated to Professor M.I. Bruce on the occasion of his 60th
birthday.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00623-8

232
H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
Scheme 1.
2. Results and discussion
ligands, which is due to the diastereotopic character of
the isopropyl groups.
The
halfsandwich-type
complex
[(p-cym)-
Although there is ample precedence for the displace-
ment of the arene ligand in compounds of the general
type [(arene)RuCl2(L)] by |- and y-donor ligands [6],
our attempts to prepare [RuCl2(SbiPr3)3] or
[RuCl2(SbiPr3)4] from 2 and excess SbiPr3 failed. Even
on prolonged heating in benzene at 80°C or on contin-
uous photolysis, no reaction between the two substrates
occurs. The same is true for the cationic derivative 3,
which is also surprisingly inert toward excess
triisopropylstibine.
RuCl2(SbiPr3)] (p-cym=p-MeC6H4CHMe2) (2), which
we considered a useful starting material for the prepa-
ration of compounds [RuCl2(SbiPr3)n] (n=3 or 4) is
obtained from [(p-cym)RuCl2]2 and three equivalents of
SbiPr3 in nearly quantitative yield. The subsequent
reaction of 2 with triisopropylstibine in the presence of
NH4PF6 leads to the formation of [(p-cym)
RuCl(SbiPr3)2]PF6 (3) (Scheme 1), which like 2, is an
orange, almost air-stable solid. Both p-cymene com-
plexes have been characterized by elemental analysis
Since further attempts to obtain a compound of the
general type [RuCl2(SbiPr3)n] by ligand substitution
from [RuCl2(SbPh3)4] and SbiPr3 equally failed, we
used RuCl3 ·3H2O as the starting material. It was
1
and spectroscopic techniques. In contrast to 2, the H-
and 13C-NMR spectra of 3 display two sets of signals
for both the protons and carbon nuclei of the SbiPr3
Scheme 2.

H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
233
Fig. 1. Molecular structure (ORTEP diagram) of compound 4.
known [7], that upon passing a stream of carbon
monoxide through a solution of RuCl3 ·3H2O in
ethanol a ‘red solution’ is formed, which reacts with
tertiary phosphines or arsines to yield mixed car-
bonyl(phosphine) or carbonyl(arsine)ruthenium com-
plexes [RuCl2(CO)n(ER3)4−n] (n=1 or 2) [8]. If this
‘red solution’ is treated with SbiPr3, a rapid change of
color from red to brown occurs and from the mixture
of products yellow, air-stable [RuCl2(CO)(SbiPr3)3] (4)
(Scheme 2) can be isolated in 40–45% yield. Both the
1H- and 13C-NMR spectra of 4 confirm that two SbiPr3
ligands are stereochemically equivalent, while the third
is not and thus a meridional configuration of the Ru(Sb
iPr3)3 moiety can be assumed.
[{Ru(p1-O2CCH3)(SbiPr3)2}2(v-O2CCH3)2(v-H2O)] [10].
The reaction of 4 with carbon monoxide proceeds
quite smoothly and affords the dicarbonyl complex
[RuCl2(CO)2(SbiPr3)2] (5) in excellent yield. Under the
conditions used, further displacement of the remaining
two stibine ligands by CO does not occur. The behavior
of 4 towards CO is thus similar to that of the com-
pounds [RuCl2(CO)(AsPh3)3] [11] and [RuH-
Cl(CO)(EPh3)3] (E=P, As) [11,12], which also undergo
a single EPh3/CO exchange. The IR spectrum of 5
displays two CO stretching frequencies at 2040 and
1910 cm−1 and this supports the structural proposal
for 5 shown in Scheme 2.
Since the spectroscopic data of 4 could not unam-
bigously decide whether the two chloro ligands are cis
or trans disposed, an X-ray crystal structure analysis
was carried out. The ORTEP plot reveals (Fig. 1) that
the geometry around the ruthenium center is distorted
octahedral with two stibine ligands trans to each other
and the third stibine trans to one chloride. The two
chlorides are in a cis arrangement. The Sb1ꢂRuꢂSb2
axis is significantly bent, which is probably due to the
steric requirements of the bulky SbiPr3 units. Whereas
the two RuꢂCl distances (Table 1) are almost identical,
the RuꢂSb bond lengths differ slightly, the shortest
being trans to Cl2. The range of the RuꢂSb distances is
very similar to that found in [Ru(p3-C3H5)2(SbiPr3)2]
[5], [RuCl2(SbPh3)4] [9] and in the dinuclear complex
Table 1
˚
Selected bond distances (A) and bond angles (°) of 4 (with estimated
S.D. in parentheses)
RuꢂSb1
RuꢂSb2
RuꢂSb3
2.662(1)
2.598(1)
2.639(1)
RuꢂC1
RuꢂCl1
RuꢂCl2
1.89(2)
2.455(3)
2.449(3)
Sb1ꢂRuꢂSb2
Sb1ꢂRuꢂC1
Sb1ꢂRuꢂSb3
Sb1ꢂRuꢂCl1
Sb1ꢂRuꢂCl2
Sb2ꢂRuꢂC1
Sb2ꢂRuꢂSb3
Sb2ꢂRuꢂCl1
102.28(3)
91.6(4)
160.82(4)
89.33(8)
78.82(9)
90.9(4)
Sb2ꢂRuꢂCl2
Sb3ꢂRuꢂCl1
Sb3ꢂRuꢂCl2
Sb3ꢂRuꢂC1
Cl1ꢂRuꢂCl2
Cl1ꢂRuꢂC1
Cl2ꢂRuꢂC1
172.8(1)
90.21(8)
82.01(9)
90.3(4)
88.0(1)
175.8(4)
96.2(4)
96.77(3)
84.91(9)

234
H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
Scheme 3.
If a solution of RuCl3 ·3H2O in ethanol is treated
instead of CO with SbiPr3, small amounts of the
chloro(hydrido)ruthenium(II) complex [RuH-
In compound 6, one of the OsꢂSb bonds is rather
labile and thus one of the stibine ligands is easily
displaced by ethene or dimethyl acetylenedicarboxylate.
Both products [OsHCl(CO)(C2H4)(SbiPr3)2] (9) and
[OsHCl(CO)(MeO2CCꢁCCO2Me)(SbiPr3)2] (10) are
white or yellow, only moderately air-sensitive solids
that are soluble in most organic solvents. The NMR
patterns for the protons and carbon atoms of the
isopropyl groups indicate that in 9 and 10 the two
stibine ligands are trans disposed. Neither on heating
nor on photolysis of 9 and 10 does an insertion of the
olefin or the alkyne into the OsꢂH bond take place.
The tris(stibine) complex 8, as well as the ethene
derivative 9, react with NaBH4 in ether/methanol or
with LiAlH4 in ether at r.t. to give the tetrahydrido
compound [OsH4(CO)(SbiPr3)2] (11). The colorless oil
did not crystallize even after it was stored for 24 h at
Cl(CO)(SbiPr3)3] (6) are formed. Upon addition of
Na2CO3 to the reaction mixture, the yield of 6 is
substantially increased to ca. 60%. Typical spectro-
scopic features of 6, which is a yellow almost air-stable
solid, are the hydride signal at l −8.36 (in C6D6) in
1
the H-NMR and the strong w(CO) band at 1900 cm−1
in the IR spectrum.
In the same manner, by using OsCl3 ·3H2O, SbiPr3
and Na2CO3 as the starting materials, the chloro(hy-
drido)osmium(II) derivative [OsHCl(CO)(SbiPr3)3] (8)
has been prepared (Scheme 3). In contrast to 6, it is a
white solid, the spectroscopic data of which are quite
similar to those of the ruthenium counterpart. The
reaction of OsCl3 ·3H2O with SbiPr3 in refluxing
ethanol produces in the absence of Na2CO3 a green
solid of composition [OsCl3(SbiPr3)3] (7), which is para-
magnetic and therefore has been characterized only by
elemental analysis. We note that related osmium(III)
complexes [OsCl3(L)3] with L=PR3, AsR3 and SbPh3
are already known and have been obtained either from
OsO4/HX or [OsX6]2− and ligand L [13]. A mer
configuration of 7 is very likely as the UV/vis spectrum
shows three bands at 16.2, 21.0 and 28.6×103 cm−1
being very similar to those obtained for the comparable
complex mer-[OsCl3(SbPh3)3] [14].
1
−78°C. The H-NMR spectrum of 11 displays, besides
a doublet for the SbCHCH3 and a septett for the
SbCHCH3 protons, a sharp singlet for the metal-
bonded hydrides at l −10.65. This chemical shift is
quite similar to that of the analogous phosphine com-
plex [OsH4(CO)(PiPr3)2] which was prepared from [Os-
HCl(CO)(PiPr3)2] and NaBH4 [15].
The results describing the reactivity of 6 towards
C2H4, CH2ꢀCHCO2Me, and NaBH4 (or LiAlH4) are
summarized in Scheme 4. Treatment of the starting
material with either ethene or methylacrylate leads to

H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
235
Scheme 4.
the displacement of one stibine ligand and to the for-
mation of the olefin complexes 12 and 13, which how-
ever are only stable in the presence of excess C2H4 or
CH2ꢀCHCO2Me, respectively. If the reaction mixtures
containing 12 and 13 are worked up by removing all
volatile substances in vacuo, the chloro(hydrido) com-
plex 6 is reformed. The spectroscopic data of the ethene
derivative are very similar to those of the osmium
compound 9, which suggests that the in situ generated
product 12 contains the hydrido and the ethene ligands
in trans disposition. Since the chemical shift of the hy-
that in the initial step, an insertion of the alkyne into
the RuꢂH bond takes place and a vinyl derivative is
formed as an intermediate. This could then react with a
second molecule of PhCꢁCH to yield 16 and styrene,
the latter has been detected by NMR spectroscopy.
The alkynyl complex 16 is quite stable and for a
short period of time can be even handled on air.
However, in THF or benzene solution, it slowly decom-
poses. As far as the NMR data of 16 are concerned, the
chemical shift and the coupling constants of the signals
of the isopropyl protons and carbon nuclei are very
similar to those of 4, and therefore, a meridional ar-
rangement of the three stibine ligands can be proposed.
The 13C-NMR spectrum of 16 displays two singlets for
the alkynyl carbon atoms at l 118.6 and 101.6, the
values being in agreement to those of the corresponding
bisphosphine ruthenium derivative [Ru(p2-O2CCH3)
(CꢁCPh)(CO)(PPh3)2] [16].
The synthesis of the allenylidene complex [RuCl2
(ꢀCꢀCꢀCPh2)(CO)(SbiPr3)2] (17) follows earlier work
by Selegue [17] and, for non-Cp containing rhodium
and ruthenium compounds, by some of us [18]. Treat-
ment of 6 in benzene with an excess of the propargylic
alcohol HCꢁCCPh2OH affords a red solution in which
the olefin CH2ꢀCHCPh2OH can be detected by 1H-
NMR spectroscopy. Since this observation is in agree-
ment with that made during the preparation of 16
(where styrene is formed as the by-product), we assume
that in the initial step of the reaction of 6 with
HCꢁCCPh2OH the functionalized alkynyl complex
[RuCl(CꢁCCPh2OH)(CO)(SbiPr3)3] is formed. Passing
a benzene solution of the crude reaction product over
acidic Al2O3 (which always contains chloride ions)
1
dride signal in the H-NMR spectrum of 13 (l −4.74)
is almost identical to that of 12 (l −4.84), we assume
that the stereochemistry of both complexes is the same.
In contrast to the olefin compounds 12 and 13, the
related alkyne complex [RuHCl(CO)(MeO2CCꢁCCO2-
Me)(SbiPr3)2] (14) is quite stable and has been isolated
as a red solid in 63% yield. Likewise to the osmium
1
counterpart, the H-NMR spectrum of 14 displays a
sharp singlet at l −3.74, which together with the IR
spectroscopic data supports the structural proposal.
The reaction of 6 with either NaBH4 (in ether/
methanol) or LiAlH4 (in ether) affords the dihydrido
complex [RuH2(CO)(SbiPr3)3] (15), which was recently
prepared in our laboratory from [RuH2(H2)(SbiPr3)3]
and CO [5]. Even if we changed the reaction conditions,
the formation of a tetrahydrido or dihydrido(dihydro-
gen) derivative analogous to 11 could not be observed.
Whereas dimethyl acetylenedicarboxylate reacts with
6 by displacement of a stibine ligand, phenylacetylene
behaves differently and upon treatment with 6 under-
goes a hydride substitution reaction to give [Ru-
Cl(CꢁCPh)(CO)(SbiPr3)3] (16) (Scheme 5). We assume

236
H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
Scheme 5.
finally gives the allenylidene compound 17 in moderate
yield. In order to rationalize the formation of 17, we
believe that by attack of H3O+ to the OH group of the
supposed RuCꢁCCPh2OH unit a cationic allenylidene
ruthenium species is generated as an intermediate,
which on substitution of SbiPr3 by Cl−, forms 17.
Characteristic features for 17 are the strong CꢀCꢀC
stretch in the IR spectrum at 1960 cm−1 and the three
low-field signals for the allenylidene carbon atoms at l
299.7, 210.2 and 149.1 in the 13C-NMR spectrum. The
chemical shift of the resonance for the RuꢀC nuclei (l
299.7) is very similar to that of the structurally related
bis(phosphine) complex [RuCl2(ꢀCꢀCꢀCPh2){s1(P)-
iPr2PCH2CO2Me}{s2(P,O)-iPr2PCH2C(O)OMe}] (l
306.2) ([18]c).
indicates that in agreement with theoretical calculations
[20] the y-acceptor character of unsaturated carbenes
such as vinylidenes or allenylidenes and of CO is nearly
the same.
3. Experimental
All experiments were carried out under an atmo-
sphere of argon by using Schlenk techniques. The start-
ing materials 1 [21] and SbiPr3 ([1]d, [22]) were
prepared by published methods. IR: Perkin-Elmer 1320,
UV/vis: Hitachi U-2000, NMR: Bruker AC 200 and
AMX 400. Melting and decomposition points were
determined by DTA.
The structural proposal for 17 has been confirmed by
an X-ray crystal structure analysis. As it is shown in
Fig. 2, the metal center is octahedrally coordinated with
the two stibine ligands trans disposed. Both the CO and
the allenylidene unit are trans to chloride, the distance
RuꢂCl1 being somewhat longer than RuꢂCl2 (Table 2).
The bond length RuꢂC1 is comparable with that of
[RuCl2(ꢀCꢀCꢀCPh2){s1(P)-iPr2PCH2CO2Me}{s2(P,
3.1. Preparation of [(p-cym)RuCl2(SbiPr3)] (2)
A solution of 423 mg (0.69 mmol) of 1 in 30 ml of
CH2Cl2 was treated with 430 ml (2.08 mmol) of SbiPr3
and stirred for 2 h at r.t. The solution was filtered and
the filtrate was brought to dryness in vacuo. After the
oily residue was layered with 10 ml of pentane, an
orange solid was formed; this was filtered and dried in
vacuo. Yield 715 mg (93%); m.p. 90°C (decomp.). Anal.
Found: C, 40.90; H, 6.11. C15H32Cl2RuSb calc.: C,
40.96; H, 6.33. 1H-NMR (400 MHz, C6D6): l 5.49, 5.38
(both d; J(HH)=5.6 Hz; 4H; C6H4), 2.98 (sept;
J(HH)=7.2 Hz; 1H; CHCH3 of p-cym), 2.41 (sept;
J(HH)=7.6 Hz; 3H; SbCHCH3), 1.91 (s; 3H;
C6H4CH3), 1.34 (d; J(HH)=7.6 Hz; 18H; SbCHCH3),
1.17 (d; J(HH)=7.2 Hz; 6H; CHCH3 of p-cym). 13C-
NMR (100.6 MHz, C6D6): l 105.2, 92.8 (both s; CCH3
and CCHCH3 of p-cym), 85.0, 80.9 (both s; CH of
C6H4), 31.0 (s; CHCH3 of p-cym), 22.5 (s; CHCH3 of
˚
O)-iPr2PCH2C(O)OMe}] (1.84(1) A) ([18]c). The two
carbon–carbon distances in the RuꢀCꢀCꢀC chain of 17
are also quite similar to those found in [RuCl2
(ꢀCꢀCꢀCPh2){s1(P) - iPr2PCH2CO2Me}{s2(P,O)-iPr2
PCH2C(O)OMe}] and other transition metal allenyli-
dene complexes [18,19]. This implies that besides the
usual bonding formulation a second resonance struc-
ture, corresponding to a zwitterionic species has to be
taken into consideration. The SbꢂRuꢂSb axis of 17 is
almost exactly linear as is the RuꢀCꢀCꢀC chain. It
should be noted that the distances between ruthenium
and the carbon atom of CO and the h-carbon atom of
the allenylidene ligand are virtually identical, which

H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
237
Fig. 2. Molecular structure (ORTEP diagram) of compound 17.
p-cym), 22.0 (s; SbCHCH3), 20.3 (s; SbCHCH3), 18.4
(s; C6H4CH3).
vacuo and after 10 ml of pentane were added, an
orange solid precipitated; it was separated from the
mother liquor and dried in vacuo. Yield 503 mg (88%);
m.p. 80°C (decomp.). Anal. Found: C, 36.15; H, 5.78.
3.2. Preparation of [(p-cym)RuCl(SbiPr3)2]PF6 (3)
1
C28H56ClF6PRuSb2 calc.: C, 36.65; H, 6.15. H-NMR
A solution of 346 mg (0.62 mmol) of 2 in 30 ml of
methanol was treated with 650 ml (3.14 mmol) of SbiPr3
and 172 mg (1.05 mmol) of NH4PF6 and stirred for 2 h
at r.t. The solvent was removed, the residue was dis-
solved in 30 ml of CH2Cl2 and the solution was filtered
with Celite. The filtrate was concentrated to ca. 1 ml in
(400 MHz, CDCl3): l 6.30, 5.98 (both d; J(HH)=6.0
Hz; 4H; C6H4), 2.61 (sept; J(HH)=7.6 Hz; 6H;
SbCHCH3), 2.56 (sept; J(HH)=7.2 Hz; 1H; CHCH3
of p-cym), 2.04 (s; 3H; C6H4CH3), 1.47, 1.44 (both d;
J(HH)=7.6 Hz; 36H; SbCHCH3), 1.25 (d; J(HH)=
7.2 Hz; 6H; CHCH3 of p-cym). 13C-NMR (100.6 MHz,
CDCl3): l 109.0, 96.5 (both s; CCH3 and CCHCH3 of
p-cym), 85.3, 80.2 (both s; CH of C6H4), 31.1 (s;
CHCH3 of p-cym), 22.7 (s; SbCHCH3), 22.3, 21.9
(both s; SbCHCH3), 21.8 (s; CHCH3 of p-cym), 19.8 (s;
C6H4CH3). 31P-NMR (162.0 MHz, CDCl3): l −144.1
(sept; J(PF)=712.8 Hz; PF6).
Table 2
˚
Selected bond distances (A) and bond angles (°) of 17 (with estimated
S.D. in parentheses)
RuꢂSb1
RuꢂSb2
RuꢂCl1
RuꢂCl2
Sb1ꢂRuꢂSb2
Sb1ꢂRuꢂC1
Sb1ꢂRuꢂCl1
Sb1ꢂRuꢂCl2
Sb1ꢂRuꢂC4
Sb2ꢂRuꢂC1
Sb2ꢂRuꢂCl1
Sb2ꢂRuꢂCl2
2.680(2)
2.679(2)
2.469(5)
2.41(2)
174.31(7)
98.8(5)
80.6(1)
89.4(3)
92(1)
RuꢂC1
RuꢂC4
C1ꢂC2
C2ꢂC3
Sb2ꢂRuꢂC4
C1ꢂRuꢂCl1
C1ꢂRuꢂCl2
Cl1ꢂRuꢂCl2
Cl1ꢂRuꢂC4
Cl2ꢂRuꢂC4
RuꢂC1ꢂC2
C1ꢂC2ꢂC3
1.88(2)
1.88(4)
1.24(2)
1.34(2)
3.3. Preparation of cis,mer-[RuCl2(CO)(SbiPr3)3] (4)
89(1)
178.6(6)
90.1(7)
88.7(5)
A slow stream of CO was passed through a solution
of 438 mg (1.68 mmol) of RuCl3 ·3H2O in 35 ml of
ethanol for 30 min at 80°C. After cooling to r.t., the
solution was treated with 1.04 ml (5.02 mmol) of SbiPr3
which led to an instantaneous change of color from red
to brown. The solution was stirred for 2 h and then
88(1)
86.8(5)
93.8(1)
89.4(3)
176(1)
177(2)
174(2)

238
H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
3.6. Preparation of [OsCl3(SbiPr3)3] (7)
concentrated to ca. 10 ml in vacuo. After it was stored
for 3 h at 25°C, a yellow solid precipitated which was
filtered, washed twice with 5-ml portions of methanol
and dried in vacuo. Yield 665 mg (42%); m.p. 66°C
(decomp.). Anal. Found: C, 34.99; H, 6.91.
C28H63Cl2ORuSb3 calc.: C, 35.29; H, 6.66. IR (C6H6):
A solution of 123 mg (0.36 mmol) of OsCl3 ·3H2O in
15 ml of ethanol was treated with 450 ml (2.17 mmol) of
SbiPr3 and heated under reflux for 1 h. A smooth
change of color from brown to green occurred. After
the solution was brought to r.t., it was concentrated to
ca. 5 ml in vacuo. A green solid precipitated which was
filtered, washed with small portions of methanol and
dried in vacuo. Yield 275 mg (73%); m.p. 78°C (de-
comp.). Anal. Found: C, 30.66; H, 6.26; Sb, 34.37.
C27H63Cl3OsSb3 calc.: C, 30.90; H, 6.50; Sb, 34.80.
w(CO) 1905 cm−1 1H-NMR (200 MHz, C6D6): l
.
2.62 (sept; J(HH)=7.3 Hz; 6H; SbCHCH3), 2.16
(sept; J(HH)=7.3 Hz; 3H; SbCHCH3), 1.58, 1.57,
1.41 (all d; J(HH)=7.3 Hz; 54H; SbCHCH3).
13C-NMR (50.3 MHz, C6D6): l 200.8 (s; CO), 24.4,
22.6, 22.4 (all s; SbCHCH3), 22.3, 22.2 (both s;
SbCHCH3).
UV/vis (CH2Cl2): 16.2, 21.0 and 28.6×103 cm−1
.
3.7. Preparation of [OsHCl(CO)(SbiPr3)3] (8)
3.4. Preparation of cis,cis,trans-[RuCl2(CO)2(SbiPr3)2]
(5)
A solution of 386 mg (1.10 mmol) of OsCl3 ·3H2O
and 1.4 ml (6.76 mmol) of SbiPr3 in 25 ml of ethanol
was heated under reflux for 1 h. A smooth change of
color from brown to green occurred. After the solution
was brought to r.t., an excess of Na2CO3 (ca. 1 g) was
added and the reaction mixture was again refluxed for
2 h. During this process, the solution became colorless.
After cooling to r.t., the solvent was removed and the
remaining residue was extracted twice with 20-ml por-
tions of pentane. The combined extracts were brought
to dryness in vacuo and the oily residue was treated
with 10 ml of methanol. A colorless solid precipitated
which was separated from the mother liquor, washed
twice with small portions of methanol (0°C) and dried
in vacuo. Yield 789 mg (71%); m.p. 103°C (decomp.).
Anal. Found: C, 33.47; H, 6.14; Sb, 36.25.
C28H64ClOOsSb3 calc.: C, 33.37; H, 6.40; Sb, 37.02. IR
A slow stream of CO was passed through a solution
of 273 mg (0.30 mmol) of 4 for 5 min at r.t. After the
solution was stirred for 20 min, the solvent was re-
moved and the residue was layered with 3 ml of
methanol (0°C). A yellow solid precipitated, which was
filtered, washed twice with 3-ml portions of methanol
(0°C) and dried in vacuo. Yield 204 mg (76%); m.p.
63°C (decomp.). Anal. Found: C, 32.82; H, 5.85.
C20H42Cl2O2RuSb2 calc.: C, 32.91; H, 5.80. IR (C6H6):
1
w(CO) 2040, 1960 cm−1. H-NMR (200 MHz, C6D6): l
2.60 (sept; J(HH)=7.3 Hz; 6H; SbCHCH3), 1.39 (d;
J(HH)=7.3 Hz; 36H; SbCHCH3).
3.5. Preparation of [RuHCl(CO)(SbiPr3)3] (6)
1
(C6H6): w(CO) 1875 cm−1. H-NMR (200 MHz, C6D6):
A solution of 1.06 g (4.04 mmol) of RuCl3 ·3H2O and
5.0 ml (24.15 mmol) of SbiPr3 in 60 ml of ethanol was
heated under reflux for 1 h and then treated with an
excess (ca. 3 g) of Na2CO3. A change of color from
brown to yellow occurred. The solution was continu-
ously refluxed for 5 h and then cooled to r.t. The
solvent was removed, the residue was extracted three
times with 20-ml portions of pentane and the combined
extracts were brought to dryness in vacuo. After the
oily residue was layered with 10 ml of methanol, a
yellow solid precipitated, which was filtered, washed
twice with 5-ml portions of methanol (0°C) and dried in
vacuo. Yield 2.30 g (62%); m.p. 55°C (decomp.). Anal.
Found: C, 36.17; H, 6.95; Sb, 39.00. C28H64ClORuSb3
calc.: C, 36.61; H, 7.02; Sb, 39.76. IR (hexane): w(CO)
l 2.42 (sept; J(HH)=7.3 Hz; 6H; SbCHCH3), 2.30
(sept; J(HH)=7.3 Hz; 3H; SbCHCH3), 1.52, 1.48, 1.43
(all d; J(HH)=7.3 Hz; 54H; SbCHCH3), −9.21 (s;
1H; OsH). 13C-NMR (50.3 MHz, C6D6): l 178.1 (s;
CO), 22.7, 22.6, 21.9 (all s; SbCHCH3), 21.8, 20.1 (both
s; SbCHCH3).
3.8. Preparation of [OsHCl(CO)(C2H4)(SbiPr3)2] (9)
A slow stream of ethene was passed through a solu-
tion of 621 mg (0.62 mmol) of 8 in 15 ml of benzene for
1 min at r.t. After the solution was stirred for 1 h, the
solvent was removed and the oily residue was treated
with 5 ml of methanol. A colorless solid precipitated
was separated from the mother liquor, washed twice
with small portions of methanol (0°C) and dried in
vacuo. Yield 427 mg (88%); m.p. 92°C (decomp.). Anal.
Found: C, 32.44; H, 5.85. C21H47ClOOsSb2 calc.: C,
1
1900 cm−1. H-NMR (400 MHz, C6D6): l 2.37 (sept;
J(HH)=7.3 Hz; 6H; SbCHCH3), 2.26 (sept; J(HH)=
7.3 Hz; 3H; SbCHCH3), 1.51, 1.50, 1.44 (all d;
J(HH)=7.3 Hz; 54H; SbCHCH3), −8.36 (s; 1H;
RuH). 13C-NMR (100.6 MHz, C6D6): l 201.5 (s; CO),
22.1, 21.8, 21.7 (all s; SbCHCH3), 21.5, 20.3 (both s;
SbCHCH3).
1
32.14; H, 6.04. IR (C6H6): w(CO) 1895 cm−1. H-NMR
(200 MHz, C6D6): l 2.85 (br s; 4H; C2H4), 2.41 (sept;
J(HH)=7.3 Hz; 6H; SbCHCH3), 1.37, 1.32 (both d;
J(HH)=7.3 Hz; 36H; SbCHCH3), −4.91 (s; 1H;

H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
239
OsH). 13C-NMR (50.3 MHz, C6D6): l 175.2 (s; CO),
28.9 (s; C2H4), 21.3, 21.2 (both s; SbCHCH3), 18.4 (s;
SbCHCH3).
vent was removed in vacuo and the residue treated with
methanol, a yellow solid was isolated, which due to the
1H-NMR spectrum was the starting material 6. 1H-
NMR data (200 MHz, C6D6) of 12: l 3.48 (s; 4H;
C2H4), 2.38 (sept; J(HH)=7.3 Hz; 6H; SbCHCH3),
1.40, 1.36 (both d; J(HH)=7.3 Hz; 36H; SbCHCH3),
−4.84 (s; 1H; RuH).
3.9. Preparation of
[OsHCl(CO)(MeO2CCꢁCCO2Me)(SbiPr3)2] (10)
A solution of 147 mg (0.15 mmol) of 8 and 35 ml
(0.28 mmol) of C2(CO2Me)2 in 10 ml of benzene was
stirred for 4 h at r.t. The solvent was removed in vacuo
and the oily residue was treated with 3 ml of methanol.
A yellow solid precipitated which was filtered, washed
with small portions of methanol (0°C) and dried in
vacuo. Yield 97 mg (72%); m.p. 70°C (decomp.). Anal.
Found: C, 34.06; H, 5.74. C25H49ClO5OsSb2 calc.: C,
33.41; H, 5.49. IR (C6H6): w(CO) 1925, w(CO2) 1700
(b) A solution of 111 mg (0.12 mmol) of 6 in 10 ml
of benzene was treated with 33 ml (0.31 mmol) of
1
methylacrylate and stirred for 5 min at r.t. The H-
NMR spectrum of the solution indicated that the olefin
complex [RuHCl(CO)(CH2ꢀCHCO2Me)(SbiPr3)2] (13)
was formed. Attempts to isolate 13 led to the reforma-
tion of the starting material 6. 1H-NMR data (200
MHz, C6D6) of 13: l 4.40 (dd; J(HH)=11.0 and 8.5
Hz; 1H; ꢀCHCO2Me), 4.13 (d; J(HH)=11.0 Hz; 1H of
CH2), 3.41 (s; 3H; OCH3), 2.74, 2.36 (both sept;
J(HH)=7.3 Hz; 6H; SbCHCH3), 1.48, 1.38, 1.33, 1.32
(all d; J(HH)=7.3 Hz; 36H; SbCHCH3), −4.74 (s;
1H; RuH), signal of one proton of the CH2 unit of 13
covered by CH2 signal of free CH2ꢀCHCO2Me.
cm−1 1H-NMR (400 MHz, C6D6): l 3.51 (s; 6H;
.
OCH3), 2.75 (sept; J(HH)=7.4 Hz; 6H; SbCHCH3),
1.41, 1.39 (both d; J(HH)=7.4 Hz; 36H; SbCHCH3),
−3.92 (s; 1H; OsH). 13C-NMR (100.6 MHz, C6D6): l
175.9 (s; CO), 156.6 (s; CO2CH3), 100.4 (s; CꢁC), 51.1
(s; CO2CH3), 21.9, 21.4 (both s; SbCHCH3), 20.2 (s;
SbCHCH3).
3.12. Preparation of
[RuHCl(CO)(MeO2CCꢁCCO2Me)(SbiPr3)2] (14)
3.10. Reaction of 8 and 9 with NaBH4 or LiAlH4
A solution of 156 mg (0.17 mmol) of 6 in 10 ml of
benzene was treated with 63 ml (0.51 mmol) of
C2(CO2Me)2 at r.t. A rapid change of color from yellow
to red occurred. After the reaction mixture was stirred
for 30 min, the solvent was removed and the oily
residue treated with 3 ml of methanol. A red solid
precipitated, which was separated from the mother
liquor, washed twice with small portions of methanol
(0°C) and dried in vacuo. Yield 87 mg (63%); m.p. 87°C
(decomp.). Anal. Found: C, 37.40; H, 5.99.
C25H49ClO5RuSb2 calc.: C, 37.09; H, 6.10. IR (THF):
A solution of either 112 mg (0.11 mmol) of 8 or 113
mg (0.14 mmol) of 9 in 15 ml of diethylether was
treated with an excess (ca. 300 mg) of NaBH4 and 2 ml
of methanol. The solution was stirred for 4 h at 60°C
and then cooled to r.t. The solvent was removed, the
residue was extracted twice with 15-ml portions of
pentane and the combined extracts were brought to
dryness in vacuo. A colorless oil was isolated, which
besides small amounts of impurities, contained the te-
trahydrido complex [OsH4(CO)(SbiPr3)2] (11) as the
main product. An alternative procedure to generate 11
is treating a solution of 117 mg (0.12 mmol) of 8 or 101
mg (0.13 mmol) of 9 in 15 ml of diethylether with an
excess (ca. 200 mg) of LiAlH4. The reaction mixture
was worked up as described above. On both routes the
yield of 11 is 85–90%. Spectroscopic data of 11: IR
1
w(CO) 1955, w(CO2) 1705 cm−1. H-NMR (200 MHz,
C6D6): l 3.48 (s; 6H; OCH3), 2.71 (sept; J(HH)=7.9
Hz; 6H; SbCHCH3), 1.43, 1.42 (both d; J(HH)=7.9
Hz; 36H; SbCHCH3), −3.74 (s; 1H; RuH).
3.13. Reaction of 6 with NaBH4 or LiAlH4
1
(C6H6): w(CO) 1935 cm−1. H-NMR (400 MHz, C6D6):
l 1.85 (sept; J(HH)=7.2 Hz; 6H; SbCHCH3), 1.22 (d;
J(HH)=7.2 Hz; 36H; SbCHCH3), −10.65 (s; 4H;
OsH). 13C-NMR (100.6 MHz, C6D6): l 182.9 (s; CO),
20.9 (s; SbCHCH3), 18.3 (s; SbCHCH3).
A solution of 117 mg (0.13 mmol) of 6 in 15 ml of
diethylether was treated with an excess (ca. 300 mg) of
NaBH4 and 3 ml of methanol and stirred for 3 h at r.t.
The solvent was removed and the residue was extracted
twice with 15 ml of pentane. The combined extracts
were brought to dryness in vacuo and after the oily
residue was treated with 3 ml of methanol, a colorless
solid was isolated. The 1H-NMR spectrum revealed
that besides small amounts of impurities, the dihydrido
complex [RuH2(CO)(SbiPr3)3] (15) was formed. It was
identified by comparison of the NMR data with those
of an authentic sample [5]. An alternative procedure to
generate 15 is treating a solution of 124 mg (0.13 mmol)
3.11. Reaction of 6 with olefins CH2ꢀCHR (R=H,
CO2Me)
(a) A slow stream of ethene was passed through a
solution of 167 mg (0.18 mmol) of 6 in 10 ml of
1
benzene for 5 min at r.t. The H-NMR spectrum of the
solution indicated that the ethene complex [RuH-
Cl(CO)(C2H4)(SbiPr3)2] (12) was formed. After the sol-

240
H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
of 6 in 15 ml of diethylether with an excess (ca. 200 mg)
of LiAlH4. After the reaction mixture was worked up as
described above, the formation of 15 was confirmed by
NMR spectroscopy.
3.16. Crystal structure analysis of 4
Single crystals were grown from ethanol. Crystal data
(from 25 reflections with 11°BUB14°): orthorhombic,
space group Pna21 (no. 33), a=23.159(3), b=
3
˚
˚
3.14. Preparation of [RuCl(CꢁCPh)(CO)(SbiPr3)3] (16)
10.314(3), c=16.134(3) A, V=3854(1) A ; Z=4,
D
calc. =1.641 g cm−3, v=2.632 mm−1. Crystal size
A solution of 213 mg (0.23 mmol) of 6 in 10 ml of
benzene was treated with 84 ml (0.76 mmol) of pheny-
lacetylene and stirred for 30 min at r.t. A smooth
change of color from yellow to red occurred. The
solvent was removed in vacuo and the oily residue
treated with 3 ml of pentane. A yellow solid precipi-
tated, which was separated from the mother liquor,
washed with 3 ml of pentane (0°C) and dried in vacuo.
Yield 134 mg (57%); m.p. 52°C (decomp.). Anal.
Found: C, 43.00; H, 6.98. C36H68ClORuSb3 calc.: C,
42.45; H, 6.73. IR (THF): w(CꢁC) 2100, w(CO) 1920
0.35×0.25×0.25 mm3. Enraf Nonius CAD4 diffrac-
˚
tometer, Mo–Kh radiation (0.71073 A), graphite
monochromator, T=293(2) K, ꢀ/U scan, max. 2U=
56°; 5521 reflections scanned, 4805 reflections indepen-
dent, 4804 included in dataset; intensity data corrected
for Lorentz and polarization effects, empirical absorp-
tion correction applied (C-scans, minimum transmis-
sion 92.35%). The structure was solved by direct
methods (SHELXS-86); atomic coordinates were
refined by full-matrix least-squares against F2o (334
parameters, SHELXL-93). The positions of the hydro-
gen atoms were calculated according to ideal geometry
cm−1 1H-NMR (200 MHz, C6D6): l 7.59–6.91 (m;
.
˚
5H; C6H5), 2.62 (sept; J(HH)=7.3 Hz; 6H;
SbCHCH3), 2.23 (sept; J(HH)=7.3 Hz; 3H;
SbCHCH3), 1.58, 1.57, 1.49 (all d; J(HH)=7.3 Hz;
54H; SbCHCH3). 13C-NMR (50.3 MHz, C6D6): l 201.1
(s; CO), 131.5, 130.3, 129.9, 125.6 (all s; C6H5), 118.6 (s;
CꢁCPh), 101.6 (CꢁCPh), 23.8, 23.6, 23.1 (all s;
SbCHCH3), 22.9, 22.8 (both s; SbCHCH3).
(distance CꢂH 0.95 A). R1=0.0355, wR2=0.0682 for
3779 observed reflections [I\2|(I)], R1=0.0710,
wR2=0.0874 for all 4804 data reflections; reflex to
parameter ratio 14.4; residual electron density +1.092/
−3
˚
−0.622 eA
.
3.17. Crystal structure analysis of 17
3.15. Preparation of
Single crystals were grown from cyclohexane. Crystal
[RuCl2(ꢀCꢀCꢀCPh2)(CO)(SbiPr3)2] (17)
data (from 25 reflections with 11°BUB14°): triclinic,
(
space group P1 (no. 2), a=8.966(3), b=13.134(4),
˚
A solution of 136 mg (0.15 mmol) of 6 in 10 ml of
benzene was treated with 0.95 ml (0.38 mmol) of a 0.4
M solution of HCꢁCCPh2OH in toluene and stirred for
1 h at r.t. A change of color from yellow to red
occurred. The solvent was removed, the residue was
dissolved in 2 ml of benzene and the solution was
chromatographed on Al2O3 (acidic, activity grade I,
length of column 7 cm). With benzene, a yellow frac-
tion was eluted that contained a mixture of products
and was discarded. A red fraction was eluted with
diethylether, which was brought to dryness in vacuo.
The residue was extracted with 30 ml of pentane, the
extract was concentrated to ca. 10 ml and then stored
for 12 h at −78°C. A red solid precipitated, which was
filtered, washed with small portions of pentane (−
20°C) and dried in vacuo. Yield 46 mg (34%); m.p.
56°C (decomp.). Anal. Found: C, 45.61; H, 6.13.
C34H52Cl2ORuSb2 calc.: C, 45.77; H, 5.87. IR (THF):
c=19.412(3) A, h=75.52(2)°, i=79.94(2)°, k=
74.25(2)°, V=2087.6(9) A ; Z=2, Dcalc=1.42 g cm−3
,
3
˚
v=1.771 mm−1. Crystal size 0.1×0.1×0.15 mm3.
Enraf Nonius CAD4 diffractometer, Mo–Kh radiation
˚
(0.71073 A), graphite monochromator, T=293 K, ‚/
U-scan, max. 2U=48°; 6098 reflections scanned, 5623
reflections independent and included in dataset; inten-
sity data corrected for Lorentz and polarization effects,
empirical absorption correction applied, minimum
transmission 80.8%. The structure was solved by direct
methods (SHELXS-86); atomic coordinates were
refined by full-matrix least-squares against F2o (371
parameters, SHELXL-93). The positions of the hydro-
gen atoms were calculated according to ideal geometry
˚
(distance CꢂH 0.95 A). The chlorine atom Cl2 and the
trans disposed carbonyl ligand were found to be disor-
dered. The alternative positions were refined isotropi-
cally with occupation factors of 0.6:0.4 for Cl2 and
0.6:0.2:0.2 for C4 and O. The unit cell contains one
solvent molecule (methylcyclohexane) which could not
be refined due to multidisordering. The five highest
peaks of the final difference Fourier synthesis are lo-
cated near to this solvent molecule. R=0.0749, Rw=
0.2022 for 2876 reflections [I\2|(I)]; R=0.1848,
Rw=0.2629 for all data reflections; reflex:parameter
ratio 15.16; residual electron density +1.439/−1.400
w(CꢀCꢀC) 1960, w(CO) 1920 cm−1 1H-NMR (200
.
MHz, C6D6): l 8.06–7.02 (m; 10H; C6H5), 2.54 (sept;
J(HH)=7.3 Hz; 6H; SbCHCH3), 1.44, 1.35 (both d;
J(HH)=7.3 Hz; 36H; SbCHCH3). 13C-NMR (50.3
MHz, C6D6): l 299.7 (s; RuꢀC), 210.2 (s; RuꢀCꢀC),
197.3 (s; CO), 149.1 (s; CPh2), 143.2 (s; ipso-C of
C6H5), 131.3, 130.8, 127.5 (all s; C6H5), 21.8, 21.5 (both
s; SbCHCH3), 21.0 (s; SbCHCH3).

H. Werner et al. / Journal of Organometallic Chemistry 565 (1998) 231–241
241
e A−3. Detailed crystallographic data (excluding struc-
˚
[8] M.I. Bruce, in: G. Wilkinson, F.G.A. Stone, E.W. Abel (Eds.),
Comprehensive Organometallic Chemistry, vol. 2, Pergamon,
Oxford, 1982, p. 693.
[9] N.R. Champness, W. Levason, M. Webster, Inorg. Chim. Acta
208 (1993) 189.
ture factors) for the structure of 4 and 17 have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication no. 101236.
Copies of the data can be obtained free of charge on
application to the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (email: deposit@
chemcrys.cam.ac.uk).
[10] C. Gru¨nwald, M. Laubender, J. Wolf, H. Werner, J. Chem. Soc.
Dalton Trans. (1998) 833.
[11] A.D. Harris, S.D. Robinson, Inorg. Chim. Acta. 42 (1980) 25.
[12] (a) P.G. Douglas, B.L. Shaw, J. Chem. Soc. A (1970) 1556. (b)
E.W. Ainscough, T.A. James, S.D. Robinson, J.N. Wingfield, J.
Organomet. Chem. 60 (1973) C63. (c) M. Preece, S.D. Robinson,
J.N. Wingfield, J. Chem. Soc. Dalton Trans. (1976) 613. (d) D.S.
Bohle, W.R. Roper, Organometallics 5 (1986) 1607. (e) S. Huh,
Y. Cho, M.-J. Jun, Polyhedron 13 (1994) 1887.
Acknowledgements
[13] W.P. Griffith, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty
(Eds.), Comprehensive Coordination Chemistry, vol. 4, Perga-
mon, Oxford, 1987, p. 573.
[14] R.A. Cipriano, W. Levason, R.A.S. Mould, D. Pletcher, M.
Webster, J. Chem. Soc. Dalton Trans. (1990) 2609.
[15] H. Werner, M.A. Esteruelas, U. Meyer, B. Wrackmeyer, Chem.
Ber. 120 (1987) 11.
We thank the Deutsche Forschungsgemeinschaft
(SFB 347) and the Fonds der Chemischen Industrie for
financial support. We also gratefully acknowledge sup-
port by B. Weberndo¨rfer for valuable assistance during
the crystallographic work, by R. Schedl and C.P. Kneis
(DTA and elemental analyses) and by Degussa AG
(gifts of chemicals).
[16] A. Santos, J. Lopez, L. Matas, J. Ros, A. Galan, A.M. Echavar-
ren, Organometallics 12 (1993) 4215.
[17] J.P. Selegue, Organometallics 1 (1982) 217.
[18] (a) H. Werner, T. Rappert, Chem. Ber. 126 (1993) 669. (b) H.
Werner, T. Rappert, R. Wiedemann, J. Wolf, N. Mahr,
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Steinert, C. Gru¨nwald, J. Wolf, Chem. Ber. 128 (1995) 49.
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H. Berke, U. Gro¨ssmann, G. Huttner, L. Zsolnai, Chem. Ber.
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