RuH2(H2)2(PCy3)2: A room temperature catalyst for the Murai reaction

Article abstract of DOI:10.1016/j.molcata.2003.10.034

RuH₂(H₂)₂(PCy₃)₂ (1) and RuH(o-C₆H₄C(O)Me)(H₂)(PCy ₃)₂ (2) or, 1 and RuH(o-C₆H₄C(O)Ph) (H₂)(PCy₃)₂ (3) were shown to be efficient catalysts for the ethylene coupling reaction with acetophenone (7a) or benzophenone (9), respectively. This efficiency under such mild conditions is attributed to the facile generation of two vacancies on the ruthenium centre. Such an hypothesis is confirmed by the fact that the corresponding carbonyl complexes RuH(o-C₆H₄C(O)Me)(CO)(PCy₃) ₂ (4) and RuH(o-C₆H₄C(O)Ph)(CO)(PCy ₃)₂ (5) were found completely inactive for the Murai coupling under the same conditions. Furthermore, we postulate that the bis(chelate) complex Ru(C₆H₄C(O)CH₃) ₂(PCy₃)₂ (6), which is the resting state of the catalyst, is responsible for the deactivation of our catalytic system.

Full text of DOI:10.1016/j.molcata.2003.10.034

Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
RuH2(H2)2(PCy3)2: a room temperature catalyst for the Murai reaction
Yannick Guaria,∗, Aida Castellanosb, Sylviane Sabo-Etienneb,1, Bruno Chaudretb
a
Laboratoire de Chimie Moléculaire et Organisation du Solide, UMR 5637 CNRS, Université de Montpellier II,
Sciences et Techniques du Languedoc, Place E. Bataillon F-34095 Montpellier Cedex 5, France
Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, F-31077 Toulouse Cedex 04, France
b
Received 23 July 2003; received in revised form 10 October 2003; accepted 31 October 2003
Abstract
RuH2(H2)2(PCy3)2 (1) and RuH(o-C6H4C(O)Me)(H2)(PCy3)2 (2) or, 1 and RuH(o-C6H4C(O)Ph)(H2)(PCy3)2 (3) were shown to be efficient
catalysts for the ethylene coupling reaction with acetophenone (7a) or benzophenone (9), respectively. This efficiency under such mild
conditions is attributed to the facile generation of two vacancies on the ruthenium centre. Such an hypothesis is confirmed by the fact that the
corresponding carbonyl complexes RuH(o-C6H4C(O)Me)(CO)(PCy3)2 (4) and RuH(o-C6H4C(O)Ph)(CO)(PCy3)2 (5) were found completely
inactivefortheMuraicouplingunderthesameconditions. Furthermore, wepostulatethatthebis(chelate)complexRu(C6H4C(O)CH3)2(PCy3)2
(6), which is the resting state of the catalyst, is responsible for the deactivation of our catalytic system.
© 2003 Elsevier B.V. All rights reserved.
Keywords: Room temperature; Catalyst; Murai reaction; Ruthenium
1. Introduction
addition of the aromatic ketone leads to an ortho-metallated
intermediate RuH[o-C6H4–C(O)R] (II). Hydrogen mi-
gration and carbon–carbon coupling would lead to the
organic product and regenerate the active species [Ru]
(I). Trost and co-workers have also studied the coupling
of olefinic substrates with ␣-unsaturated esters catalysed
by RuH2(CO)(PPh3)3 [12]. They proposed that the active
species [Ru] is formed both by hydrogenation of an in-
coming olefin and elimination of carbon monoxide via the
formation of an unsaturated species [Ru]S(PPh3)3 where
S is a solvent molecule coordinated to the ruthenium
centre.
In 1998, we reported briefly that the complexes RuH2
(H2)2(PCy3)2 (1) and RuH(o-C6H4C(O)Me)(H2)(PCy3)2
(2) were efficient catalysts for the coupling between ace-
tophenone and ethylene at room temperature [13]. A recent
study using 1 as catalyst for the coupling of different
para-substituted acetophenone derivatives with ethylene
has been performed by others [14]. Deactivation of the cat-
alyst was discussed and ligand dissociation was proposed
to play an important role but without further insights into
this phenomenon. We now wish to report our unpublished
results [15] concerning the catalytic activity and deacti-
vation pathways for the coupling of acetophenone (and
para-substituted acetophenones) or benzophenone with
ethylene using the ruthenium catalyst precursors 1 and
During the past 20 years, intense research activity has
been devoted to the catalytic activation of carbon–hydrogen
bonds leading to the formation of new carbon–carbon bonds
as an interesting and important alternative to coupling reac-
tions involving halide derivatives. The new carbon–carbon
bond can be formed via insertion of carbon monoxide,
isocyanide, alkynes or alkenes into the carbon–hydrogen
bond [1–4]. In 1993, Murai and co-workers reported the
alkylation of aromatic ketones via the insertion of alkenes
into a carbon–hydrogen bond by using ruthenium cata-
lyst precursors, RuH2(CO)(PPh3)3 being the most efficient
[5–7]. This fairly general system, which requires reaction
temperature at or above 130 ◦C, has been extended to a
variety of aromatic and olefinic substrates [1,8–11]. The
mechanism proposed by Murai and co-workers (Scheme 1)
involves in a first step the formation of an intermediate
16-electron ruthenium(0) complex (I) produced by hydro-
genation of the incoming olefin, and in a second step, the
∗
Corresponding author. Tel.: +33-4-6714-4224;
fax: +33-4-6714-3852.
E-mail addresses: guari@univ-montp2.fr (Y. Guari),
sabo@lcc-toulouse.fr (S. Sabo-Etienne).
1
Fax: +33-5-6155-3003.
1381-1169/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2003.10.034

78
Y. Guari et al. / Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
R
O
R
In that case, the reaction was less selective, leading to
4% of the 1:1 adduct 10a and 96% of the 1:2 adduct 10b
(Scheme 2).
RuH2(CO)(PPh3)3
C
C
O
[Ru]
We have previously mentioned in a preliminary communi-
cation [13] the synthesis and characterization of the or-
thometallated complexes 2 and 3. These hydrido(dihydrogen)
complexes display unusual spectroscopic and dynamic
features. At room temperature, the hydride and the dihy-
drogen ligands are in fast exchange, but NMR experiments
at low temperatures demonstrate the presence of both quan-
tum mechanical and classical exchange processes between
these two ligands. However, due to the low solubility of
2 and 3, this phenomenon was only fully studied with the
analogous phenylpyridine complexes [15,16]. As 2 and 3
result from the direct reaction of 7a or 9 with 1, it was
thus interesting to test their catalytic activity in the cor-
responding coupling reactions of 7a and 9 with ethylene.
In these cases, similar conversions were obtained when
using 1 and 2 for the alkylation of 7a or 1 and 3 for the
alkylation of 9. As mentioned in the introduction, such
ortho-metallated complexes were proposed to be true inter-
mediates in the catalytic cycle of the coupling of aromatic
ketones with alkenes by Murai and co-workers. We were
able to isolate the corresponding ortho-metallated carbonyl
complexes RuH(o-C6H4C(O)R)(CO)(PCy3)2 (R = Me, 4;
R = Ph, 5) and to test them as catalysts. Remarkably, no
conversion was obtained. It is noteworthy that the analogous
complexes RuH(o-C6H4C(O)Ph)(CO)(dcypb) (with dcypb
= Cy2P(CH2)4PCy2) [17] and RuH(o-C6H4C(O)Me)(CO)
(PPh3)2 [18] have been reported to be respectively poorly
active and completely inactive for the Murai coupling.
In order to gain more information on our catalytic system,
we have performed a detailed study by varying the following
parameters: temperature, solvent, catalyst/ketone ratio and
substituents effects on the para-position of the aromatic ring
of the ketone. This study was done using 1 as catalyst pre-
cursor, acetophenone and ethylene. A catalytic experiment
was also carried out in cyclohexane-d12 and followed by 1H
NMR spectroscopy.
Y
(I)
R
R
C
C
O
O
Ru
Ru
(II)
H
Y
R
C
O
Ru
Y
H
Y
Scheme 1. Catalytic cycle proposed for the Murai reaction.
RuH(o-C6H4C(O)R)(H2)(PCy3)2 (R = Me, (2); R = Ph, (3)
respectively). The deactivation pathway will be discussed
in details.
2. Results and discussion
We have performed a series of reactions that are depicted
in Scheme 2. Total conversion of acetophenone (7a) was
achieved after 22 h by exposing a pentane suspension of
1 to 20 bar of ethylene. The 1:1 coupling product 8a was
formed exclusively. A longer reaction time (48 h.) was nec-
essary to observe the total conversion of 10 equivalents
of benzophenone (9) in the same experimental conditions.
R’
CH3
O
CH3
O
(1)
R
R
C
C
+
2.1. Influence of the temperature
Catalytic experiments were carried out at 18, 50 and 80 ◦C
in pentane. The results are reported in Fig. 1.
(8a); R=R’=H
(7a); R=H
(7b); R=Cl
(7c); R=CH3
(8’a); R=H, R’=Et
(8b); R=Cl, R’=H
(8c); R=CH3, R’=H
(8d); R=OCH3, R’=H
As can be seen, the initial rate of the reaction slightly
increases with increasing the temperature. However, the
major drawback of using a higher temperature is the de-
crease of the conversion of 7a–8a which drops to 42% at
50 ◦C and 25% at 80 ◦C. We noted that the initial colourless
solution turned brown-orange as the catalysis proceeded that
the activity ceased with the concomitant development of an
intense purple colouring of the solution. This purple colour
appeared more rapidly when increasing the temperature,
which led us to the conclusion that the deactivation pro-
cess was directly linked to the formation a purple coloured
species.
(7d); R=OCH3
(1)
C
O
C
+
R’
O
(9)
(10a); R=H
(10b); R=CH2CH3
Scheme 2. Murai coupling between ethylene and para-substituted ace-
tophenone or benzophenone using 1 as catalyst.

Y. Guari et al. / Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
79
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
0
400
800
1200
0
400
800
1200
Time (min.)
Time (min.)
Fig. 1. Acetophenone conversion vs. time at 18 ◦C (᭺), 50 ◦C (ᮀ) and
80 ◦C (×).
Fig. 3. para-substituted acetophenone conversion vs. time with R H (᭺),
=
=
=
=
R Cl (×), R Me (ᮀ) and R MeO (ꢀ).
coordinate to the ruthenium centre and stabilize the in-
termediates in the catalytic cycle, we noted a decrease in
the initial rate of the catalytic reaction and a lowering of
the conversion. Furthermore, when tetrahydrofurane was
used as a solvent, a loss in selectivity was also observed
leading to the formation of the coupling 1:2 by-product
2,6-ethylacetophenone (8ꢁa) (8a:8ꢁa in a ratio of 5.7:1). This
might be attributed to the coordination of the solvent to the
unsaturated fragment leading to some extent to the stabi-
lization of an intermediate species and thus to a decrease of
both the activity and the selectivity.
2.2. Influence of the solvent
We have performed several catalytic experiments using
pentane, cyclohexane, toluene, tetrahydrofurane and diethyl
ether as solvents at 18 ◦C. The results are reported in Fig. 2.
As can be seen from the Figure, the efficiency of this
catalytic system is optimum when performed in cyclic or
aliphatic alkanes. The initial reaction rate is not affected
when performing the reaction in toluene. However, deactiva-
tion of the catalyst is observed in that case, probably as the
result of the formation of an arene species. Indeed, as pre-
viously shown, 1 can react with unsaturated hydrocarbons
to give ␲-arene complexes [19,20]. When using solvents
such as tetrahydrofurane or diethyl ether that can easily
2.3. Influence of the substituent using para-substituted
acetophenones
The catalytic experiments were done in pentane at 18 ◦C
for all the substrates RC6H4C(O)Me (R = H, 7a; R = Cl,
7b; R = Me, 7c; R = OMe, 7d). The results are reported in
Fig. 3.
100
90
80
70
60
50
40
30
20
10
0
As mentioned earlier, catalytic experiments using the
para-subtituted acetophenone substrates 7a–d have been al-
ready reported by Busch and Leitner [14]. Our initial rates
reflect the same order of reactivity H ≈ CH3 > Cl > CH3O.
However, we do not observe any 1:2 coupling by-product.
Furthermore, the yield determined by GC/MS after only 5 h
are higher than those reported by Leitner and co-workers
after 22 h which confirms the coordinating role of toluene
in their system. When comparing the electron-donating sub-
stituent CH3 and the electron-withdrawing substituent Cl,
faster initial rate and higher total conversion of the substrate
are observed for the latter. However, we have measured a
dramatic decrease on both the conversion and the initial
rate when the para-substituent is CH3O instead of Cl. We
thus suggest that the electron-withdrawing effect is not
sufficient to explain such a behaviour and that, electronic
effects including the acetyl group, which acts as a chelating
assistant, should be invoked to explain such a result.
0
400
800
1200
Time (min.)
Fig. 2. Acetophenone conversion leading to 8a vs. time in pentane (᭺),
cyclohexane (᭛), toluene (ᮀ), tetrahydrofurane (ꢀ) and diethylether (×)
and acetophenone conversion leading to 8ꢁa vs. time in tetrahydrofurane
(
).

80
Y. Guari et al. / Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
containing two tricyclohexylphosphine in a trans posi-
100
90
80
70
60
50
40
30
20
10
0
tion and an ortho-metallated acetophenone ligand. As the
presence of ethylene coordinated to the ruthenium can-
not be excluded, the corresponding 18-electron species
RuH(o-C6H4C(O)CH3)(C2H4)(PCy3)2 with ethylene as
ligand should also be considered. Our attempts to synthe-
size this compound by bubbling ethylene through a solu-
tion of RuH(o-C6H4C(O)Me)(H2)(PCy3)2 (2) in pentane
without further addition of 7a failed, leading to complete
decomposition of the starting complex. Such a 16-electron
ortho-metallated RuH[o-C6H4-C(O)R] (II) complex was
proposed to be the true intermediate in the catalytic cycle
by Murai and co-workers [5–7]. Considering the ruthenium
precursor they used, RuH2(CO)(PPh3)3, and referring to the
work of Trost and co-workers [12], decoordination of car-
bon monoxide is thus necessary. In our case, the formation
of an unsaturated species (A) can be achieved via hydro-
genation of a second incoming olefin. This is in agreement
with the efficiency of our system at room temperature us-
ing either complexes 1, 2 or 3, as compared to the Murai’s
system operating at 135 ◦C with RuH2(CO)(PPh3)3. In our
system, vacancy sites on the ruthenium centre are easily
available by decoordination of the H2 ligand. This is not
the case when using the carbonyl complexes 4 and 5 as cat-
alyst precursors for the coupling of aromatic ketones with
olefinic substrates at room temperature.
0
400
800
1200
Time (min.)
Fig. 4. Acetophenone conversion vs. time with a catalyst (1)/substrate
(7a) ratio of 1/10 (᭺), 1/50 (ᮀ) and 1/100 (ꢀ).
2.4. Influence of the catalyst (1)/substrate (7a) ratio
The 1/10 (1/7a) ratio was chosen for direct comparison
with the experiments performed by Murai and co-workers.
We have also done some experiments in pentane at 18 ◦C
with 1/50 and 1/100 ratios and a constant 1/ethylene ratio.
The results are depicted in Fig. 4.
For the 1/100 ratio, almost no conversion was observed.
When a sample of the catalytic mixture was taken immedi-
ately after pressurization under ethylene, we noted that the
resulting solution was already purple. When a 1/50 ratio
was used, only 10% of 7a was converted to 8a, which cor-
responds to only 5 catalytic cycles while in the meantime
10 catalytic cycles were obtained for the 1/10 ratio. These
results suggest that the inhibition of the catalytic cycle is
directly linked to the amount of the starting ketone.
2.6. Deactivation pathway
Leitner and co-workers have proposed that the decoor-
dination of a tricyclohexylphosphine is responsible for the
deactivation of their catalytic system [14]. However, we
have observed that the presence of free PCy3 is detectable
only after the catalytic conversion has ceased. Such an ob-
servation can be attributed to the partial decomposition of
the catalyst when all the ketone substrate has been con-
sumed. A similar behaviour was obtained when bubbling
ethylene in a pentane solution of 2 without adding further
7a. Furthermore, from the results we have obtained, it is
clear that the deactivation of the system is directly correlated
with the formation of a purple ruthenium species, which is
strongly favoured when the temperature or the amount of
7a have increased. It is noteworthy that such a species is
formed progressively whereas the catalytic system is still
active. Finally, we have observed that once the system is
inactive, pressurisation under 20 bar of dihydrogen leads
to the regeneration of the catalyst. The orange colour is
restored and after flushing the dihydrogen atmosphere with
argon and then ethylene, the catalysis proceeds. In order
to clarify this deactivation pathway, we have performed the
following synthesis: a large excess of 7a was added to a
pentane solution of 1, leading after 24 h to compound 2
as characterized by NMR. Ethylene was then bubbled for
30 min and the mixture was stirred for 3 days. A purple
precipitate identified as Ru(C6H4C(O)CH3)2(PCy3)2 (6)
was obtained and isolated (see Scheme 3).
2.5. Catalytic pathway
In order to gain more information on the catalytic path-
way, several experiments were performed in the same ex-
perimental conditions but using cyclohexane-d12 as solvent
(see Section 4). The catalytic reaction was stopped after
10 min and an NMR tube was filled with the resulting so-
1
lution and monitored by H NMR. The spectrum shows in
addition to the signals attributed to 7a (or 8a), a triplet at
−13.70 ppm attributed to an hydride ligand with a 2JP–H
=
25.2 Hz. Multiplets are observed at 8.61, 7.86, 7.47 and
7.08 attributed to the aromatic ring of an ortho-metallated
acetophenone ligand with a signal at 2.50 ppm attributed to
the methyl group. Complex 1 is known to react with ethy-
lene to give [RuH{␩3-C6H8)PCy2}(C2H4)(PCy3)2], [21]
however no signal corresponding to the partial dehydro-
genation of the cyclohexyl groups of PCy3 was observed.
We proposed that this ruthenium species corresponds to
a 16-electron hydride RuH(o-C6H4C(O)CH3)(PCy3)2 (A)

Y. Guari et al. / Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
81
PCy3
PCy3
Ru
PCy3
Ru
H
O
O
H
H
H
(7a)
H
Ru
H
H
O
H
H
PCy3
PCy3
PCy3
(1)
(2)
(6)
Scheme 3. Synthesis of complexes 2 and 6.
The 1H NMR spectrum of 6 displays signals at 9.20, 7.58,
7.02 and 6.80 ppm attributed to the phenyl ring and a signal
at 2.53 ppm attributed to the methyl group of the orthomet-
allated acetophenone. The 31P NMR displays one signal at
21.2 ppm. It should be noticed that bubbling for 20 min di-
hydrogen through a C6D6 solution of 6 led back to a mix-
ture of the dihydrogen complexes 1 and 2. Moreover, when
a C6D6 solution of 6 was pressurised under 3 bar H2, we ob-
served quantitative formation of 1 and free actophenone as
shown by 1H and 31P NMR spectra. Such an observation is
compatible with the possibility to regenerate the catalyst un-
der dihydrogen atmosphere. Finally, it must be pointed out
that 6 was found inactive for the coupling reaction. All these
observations led us to the conclusion that, even if we cannot
completely exclude partial decomposition of the catalyst by
PCy3 decoordination, complex 6 is the resting state of the
catalyst and is responsible for the progressive main deacti-
vation pathway of this catalytic system using 1 as catalyst
precursor.
thoroughly degassed under argon before use. Microanalyses
were performed by the Laboratoire de Chimie de Coordina-
tion Microanalytical Service. NMR Spectra were recorded
on a Bruker AC 200 (at 200.13 MHz for 1H, at 81.015 MHz
for 31P and at 50.324 MHz for 13C), on a Bruker AM250 (at
1
250 MHz for H, at 101.25 MHz for 31P and at 62.89 MHz
for 13C) and on a Bruker AMX400 (at 400.13 MHz for
1H, at 161.21 MHz for 31P and at 100.71 MHz for 13C),
all these spectrometers operating on the Fourier transform
mode. FT-IR spectra were collected on a Perkin-Elmer
1725 FT-IR spectrometer. RuCl3·3H2O was purchased form
Johnson Matthey Ltd. RuH2(H2)2(PCy3)2 (1) was made
according to the procedure described in ref [22].
4.2. Ruthenium complexes
4.2.1. Synthesis of RuH(o-C6H4C(O)CH3)(H2)(PCy3)2 (2)
To a suspension of RuH2(H2)2(PCy3)2 (1) (120 mg,
0.18 mmol) in 20 ml pentane was added acetophenone
(23 ␮l, 0.20 mmol) at room temperature. The reaction was
allowed to react for 24 h during which a brown-orange solid
precipitated. The solid was then filtered off, washed with
20 ml of pentane and dried in vacuo. Yield ca. 92%. Anal.
Calcd for RuC44H76P2O: C, 67.39; H, 9.77. Found: C,
3. Conclusions
We have demonstrated the efficiency of complexes 1, 2
and 3 as catalyst precursors for the regioselective coupling
between aromatic ketones and ethylene at room tempera-
ture in pentane. The efficiency of our catalysts under such
mild conditions compared to the use of RuH2(CO)(PPh3)3 at
135 ◦C is attributed to the easier generation of two vacancies
on the ruthenium centre. In our case, the unsaturated ruthe-
nium species (A) can be obtained via hydrogenation of two
incoming olefins while decoordination of carbon monox-
ide, in addition to hydrogenation of one incoming olefin, is
necessary when using RuH2(CO)(PPh3)3. Furthermore, we
propose that the bis(chelate) complex 6 is the resting state
of the catalyst and is responsible for the progressive main
deactivation pathway when using our catalysts.
1
66.68; H, 9.84. IR (cm−1, nujol): 2022 (νRu–H). H NMR
(200.13 MHz, C6D6, 296 K; δ, ppm): 8.60 (br), 7.68 (br),
7.08 (br), 6.90 (br)(4H, Ph); 2.54 (br, 3H, CH3); −9.02 (br,
3H, RuH(H2)). 31P{1H} NMR (81.01 MHz, C6D6, 296 K;
δ, ppm): 48.0 (s). T1(min) (250 MHz, C7D8, 193 K): δ
31 ms, δ−14.9: 85 ms.
:
−5.6
4.2.2. Synthesis of RuH(o-C6H4C(O)C6H5)(H2)(PCy3)2
(3)
To a suspension of RuH2(H2)2(PCy3)2 (1) (190 mg,
0.28 mmol) in 20 ml of pentane was added benzophenone
(52 mg, 0.31 mmol) at room temperature. The reaction was
allowed to react for 24 h during which a brown-orange
solid precipitated. The solid was then filtered off, washed
with 20 ml of pentane and dried in vacuo. Yield ca. 92%.
Anal. Calcd for RuC49H78P2O: C, 69.55; H, 9.29. Found:
C, 69.59; H, 9.51. IR (cm−1, nujol): 1983 (νRu–H). 1H
NMR (200.13 MHz, C6D6, 296 K; δ, ppm): 8.08 (br),
7.15 (m)(9H, C6H4C(O)C6H5); −8.59 (br, 3H, RuH(H2)).
31P{1H} NMR (81.01 MHz, C6D6, 296 K; δ, ppm):
48.1 (s).
4. Experimental section
4.1. General methods
All reactions were carried out under argon by using
Schlenk glassware and vacuum line techniques. All solvents
were freshly distilled from standard drying agents and

82
Y. Guari et al. / Journal of Molecular Catalysis A: Chemical 212 (2004) 77–82
4.2.3. Synthesis of RuH(o-C6H4C(O)CH3)(CO)(PCy3)2 (4)
Carbon monoxyde was bubbled through a suspension of
RuH(C6H4C(O)CH3)(H2)(PCy3)2 (2) (347 mg, 0.43 mmol)
in 20 ml of pentane. The reaction was allowed to react for
5 min during which an orange solid precipitated. The or-
ange precipitate was then filtered off, washed with 20 ml of
pentane and dried in vacuo. Yield ca. 64%. Anal. Calcd for
RuC45H74P2O2: C, 66.72; H, 9.21. Found: C, 66.90; H, 9.23.
in pentane. The mixture was then transferred via canula
to an autoclave. The solution was stirred at 750 tr/min at
18 ◦C and pressurized under 20 bar of ethylene for 22 h.
The catalyst/ketone/ethylene ratio was 1/10/800. The re-
spective ratios reactant/monoalkylated product/dialkylated
product were determined by GC analysis on a Hewlett
Packard 5890 series II using a methylsilicon capillary col-
umn (30 m × 0.32 mm). GC–MS analysis was performed
on a Hewlett Packard 5890 using a methylsilicon capillary
column (12 m × 0.2 mm) coupled with a Hewlett Packard
5970 MSD using the electronic impact at 70 eV.
1
IR (cm−1, nujol): 1879 (νRu–CO). H NMR (200.13 MHz,
CDCl3, 296 K; δ, ppm): 7.96 (d, 1H, JHH = 7.3 Hz), 7.66
(d, 1H, JHH = 7.8 Hz), 7.00 (d, 1H, JHH = 7.2 Hz), 6.86 (d,
1H, JHH = 7.9 Hz)(C6H4); 2.50 (m, CH3); −16.03 (t, 1H,
JPH = 23.4 Hz, Ru–H). 31P{1H(PCy3)} NMR (81.01 MHz,
CDCl3, 296 K; δ, ppm): 41.9 (d, JPH = 23 Hz). 13C{1H}
NMR (100.62 MHz, CDCl3, 296 K; δ, ppm): 207.9 (s,
Ru(CO) or RuC(Ph)), 207.0 (s, Ru(CO) or RuC(Ph)), 206.0
(s, RuC(O)Me), 145.4 (s), 143.3 (s), 129.2 (s), 128.2 (s),
119.9 (s)(C6H4), 24.8 (s, CH3).
Acknowledgements
Financial support from the CNRS and SHELL Interna-
tional Chemicals B. V. (Amsterdam) is gratefully acknowl-
edged.
4.2.4. Synthesis of RuH(o-C6H4C(O)C6H5)(CO)(PCy3)2
(5)
References
Carbon monoxyde was bubbled through a solution of
RuH(C6H4C(O)C6H5)(H2)(PCy3)2 (3) (43 mg, 0.51 mmol)
in toluene (20 ml). A red solid is obtained in ca. 67% yield.
Anal. Calcd for RuC50H76P2O2: C, 68.86; H, 8.78. Found:
C, 68.84; H, 8.43. IR (cm−1, nujol): 1902 (νRu–CO). 1H
NMR (400.13 MHz, CDCl3, 296 K; δ, ppm): 8.05 (d, 1H,
JHH = 7.4 Hz), 7.72 (d, 1H, JHH = 7.8 Hz), 7.59 (m, 2H),
7.48 (m, 3H), 7.04 (t, 1H, JHH = 7.2 Hz), 6.86 (t, 1H,
[1] F. Kakiuchi, S. Murai, Acc. Chem. Res. 35 (2002) 826.
[2] V. Ritleng, C. Sirlin, M. Pfeffer, Chem. Rev. 102 (2002) 1731.
[3] Y. Guari, S. Sabo-Etienne, B. Chaudret, Eur. J. Inorg. Chem. 7 (1999)
1047.
[4] G. Dyker, Angew. Chem. Int. Ed. 38 (1999) 1698.
[5] S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda,
W. Chatani, Nature 366 (1993) 529.
[6] S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda,
N. Chatani, Pure Appl. Chem. 66 (1994) 1527.
[7] F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N.
Chatani, S. Murai, Bull. Chem. Soc. Jpn. 62 (1995) 681.
[8] F. Kakiuchi, Y. Yamamoto, N. Chatani, S. Murai, Chem. Lett. 8
(1995) 681.
[9] F. Kakiuchi, Y. Tanaka, T. Sato, N. Chatani, S. Murai, Chem. Lett.
8 (1995) 679.
[10] M. Sonoda, F. Kakiuchi, A. Kamatani, N. Chatani, S. Murai, Chem.
Lett. 2 (1996) 113.
[11] F. Kakiuchi, M. Yamanchi, N. Chatani, S. Murai, Chem. Lett. 2
(1996) 111.
[12] B.M. Trost, K. Imi, I.W. Davies, J. Am. Chem. Soc. 117 (1995)
5371.
JHH = 7.4 Hz)(C6H4C(O)C6H5); −15.36 (t, 1H, JPH
=
23.8 Hz, RuH). 31P{1H(PCy3)} NMR (81.01 MHz, C7D8,
296 K; δ, ppm): 42.1 (d, JPH = 24 Hz). 13C{1H} NMR
(100.62 MHz, CDCl3, 296 K; δ, ppm): 210.7 (t, Ru(CO) or
RuC(Ph), JCP = 12.3 Hz), 206.3 (t, Ru(CO) or RuC(Ph),
JCP = 12.4 Hz), 203.6 (s, RuC(O)Ph), 144.3 (s), 143.4 (s),
139.6 (s), 132.7 (s), 128.9 (s), 128.5 (s), 128.0 (s), 119.7
(s) (C6H4C(O)C6H5). T1(min) (250 MHz, CD2Cl2, 233 K)
= 139 ms.
4.2.5. Synthesis of Ru(C6H4C(O)CH3)2(PCy3)2 (6)
[13] Y. Guari, S. Sabo-Etienne, B. Chaudret, J. Am. Chem. Soc. 120
(1998) 4228.
[14] S. Busch, W. Leitner, Adv. Synth. Catal. 343 (2001) 192.
[15] Y. Guari, Ph.D. Thesis, Université Paul Sabatier III, Toulouse,
1998.
[16] J. Matthes, S. Grundemann, A. Toner, Y. Guari, B. Donnadieu, S.
Sabo-Etienne, E. Clot, H.-H. Limbach, B. Chaudret, in press.
[17] S.D. Drouin, D. Amoroso, G.P.A. Yap, D.E. Fogg, Organometallics
21 (2002) 1042.
[18] R.F.R. Jazzar, M.F. Mahon, M.K. Whittlesey, Organometallics 20
(2001) 3745.
[19] T. Arliguie, B. Chaudret, J. Chem. Soc. Chem. Commun. 13 (1986)
985.
[20] A.F. Borowski, S. Sabo-Etienne, B. Chaudret, J. Mol. Catal. A:
Chem. 174 (2001) 69.
[21] M.L. Christ, S. Sabo-Etienne, B. Chaudret, Organometallics 14
(1995) 1082.
About 37.5 equivalents of 7a (0.65 ml, 6 mmol) were
added to a solution of 1 (109.6 mg, 0.16 mmol) in pentane
(15 ml) and stirred for 24 h to afford 2 as an orange pre-
cipitate. Then, ethylene was bubbled for 30 min and the so-
lution let stirred for 3 days affording a purple precipitate
identified as 6. Anal. Calcd for RuC52H74P2O2: C, 69.38;
1
H, 8.90. Found: C, 69.40; H, 8.45. H NMR (200.13 MHz,
C6D6, 296 K; δ, ppm): 9.20 (d, 7 Hz, 2H, C6H4), 7.58 (d,
7 Hz, 2H, C6H4), 7.02 (t, 7 Hz, 2H, C6H4), 6.80 (t, 7 Hz,
2H, C6H4), 2.55 (s, 6H, CH3), 2.00–0.90 (m, 66H, PCy3).
31P{1H} NMR (81.01 MHz, C6D6, 296 K; δ, ppm): 21.2 (s).
4.3. Catalytic tests
A typical experiment was done as follows: 10 equiva-
lents of a ketone were added to a suspension of the catalyst
[22] A.F. Borowsky, S. Sabo-Etienne, M.L. Christ, B. Donnadieu, B.
Chaudret, Organometallics 15 (1996) 1427.