Mixed (P=S/P=O)-stabilized geminal dianion: Facile diastereoselective intramolecular C-H activations by a related ruthenium-carbene complex

Article abstract of DOI:10.1002/chem.201202680

A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards Ru^II was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated Ru^II complex through C-H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C-H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru ^II complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.

Full text of DOI:10.1002/chem.201202680

DOI: 10.1002/chem.201202680
Mixed (P=S/P=O)-Stabilized Geminal Dianion: Facile Diastereoselective
ꢀ
Intramolecular C H Activations by a Related Ruthenium–Carbene Complex
Hadrien Heuclin,[a] Xavier F. Le Goff,[a] and Nicolas Mꢀzailles*[a, b]
In memory of Pascal Le Floch
Abstract: A new unsymmetrical gemi-
nal dianion that contained both a phos-
phine oxide moiety and a phosphine
sulfide moiety has been synthesized. Its
reactivity towards RuII was explored,
which led to the formation of a highly
reactive carbene complex that evolved
at room temperature to yield a kinetic
orthometalated RuII complex through
the phosphine oxide moiety. This inser-
tion was found to be thermally reversi-
namic orthometalated RuII complex in
a diastereospecific manner. DFT calcu-
lations fully rationalized the experi-
mental findings in terms of the relative
energies of the kinetic and thermody-
namic products and allowed the mech-
anism of this process to be fully under-
stood.
ꢀ
ble and a second C H insertion occur-
red at a phenyl group of the phosphine
sulfide moiety to form the thermody-
Keywords: carbenes · coordination
modes · density functional calcula-
tions · dianions · ruthenium
ꢀ
C H activation of the phenyl group of
Introduction
The use of phosphorus-stabilized geminal dianions[1] as pre-
cursors of carbene complexes has emerged as a powerful
synthetic tool over the past decade. Part of the interest in
using such species lays in their potential donation of the
four electrons in the metal–carbon interactions. As a conse-
quence, carbene complexes of not only transition metals[2]
and main-group elements,[3] but also of rare-earth metals[4,5]
and actinides,[6] have been synthesized with ligands 1Li2
–
[7]
3Li2
.
These latter cases have been studied in great details
because the understanding of the electronic nature of the
M=C bond, as well as its reactivity, is of fundamental inter-
est. An alternative approach to these complexes relies on
the double deprotonation of the coordinated neutral ligand,
although it requires the synthesis of a precursor complex
that features two strongly basic ligands. Theoretical calcula-
tions on two dianionic species, 1Li2 and 3Li2 (Scheme 1), have
shown that the stabilization of the two lone pairs on the
same carbon atom depends, to the greatest extent, on the
different substituents on the phosphorus atom, through the
Scheme 1. Coordination patterns of the geminal dianions to metal cen-
ters.
[1f]
ꢀ
accepting antibonding P X orbitals. Not surprisingly then,
the stabilization by the PPh2=S moiety appeared to be
weaker than that by the P(OR)2=O moiety. In turn, the
overall donation toward the metal center will be in competi-
tion with the stabilization by the substituent at the carbon
center; that is, the stronger the stabilization is, the weaker
the donation will be. Thus, it is of interest to have access to
a wide range of dianions to be able to finely tune these pa-
rameters. These dianions possess the important additional
feature of being tridentate ligands. Thus, we envisaged that
the chemistry at the metal could also be tuned by the
[a] H. Heuclin, Dr. X. F. Le Goff, Dr. N. Mꢀzailles
Laboratoire Hꢀtꢀroꢀlꢀments et Coordination
Ecole Polytechnique, CNRS
Route de Saclay, 91120 Palaiseau (France)
[b] Dr. N. Mꢀzailles
Current address: Laboratoire Hꢀtꢀrochimie Fondamentale
et Appliquꢀe, Universitꢀ Paul Sabatier, CNRS
118 Route de Narbonne, 31062 Toulouse cedex 9 (France)
Fax : (+33)561558204
E-mail: mezailles@chimie.ups-tlse.fr
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201202680.
ꢀ
strength of the X M bond. This new property relies on
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FULL PAPER
access to a geminal dianion of mixed P=S/Y ligands, for
which only two examples have been reported so far (4aLi2
:
Y=PPh2NSiMe3,[1j] 4bLi2: Y=SO2Ph).[1k]
Herein, in the first part, we report the synthesis of the
monoanion and geminal dianion of a mixed P=S/P=O
ligand. The coordination behavior of the dianion with a RuII
precursor is then reported. An unprecedented room-temper-
ꢀ
ature C H activation on a phenyl ring of the PPh2=O
ꢀ
moiety, in a diastereospecific fashion, was observed. This C
ꢀ
H activation was thermally reversible and a second C H ac-
tivation occurred on a phenyl ring of the PPh2=S moiety,
also in diastereospecific manner. A comprehensive DFT
study was performed to rationalize these experimental find-
ings and the results are also presented herein.
Scheme 3. Synthesis of compounds 6Li and 6Li2
.
lated and showed poor solubility in common solvents. How-
ever, it was highly soluble in pyridine, which allowed its
characterization by multinuclear NMR spectroscopy. In its
31P NMR spectrum, an AB system at d=35.3 and 33.8 ppm
Results and Discussion
(2J
1H NMR spectrum, a broad doublet (2J
d=2.33 ppm, which corresponded to
22.3 ppm (dd, 1J(P,C)=105 Hz, 1J
(P,C)=135 Hz) in the
ACHTUNGTRENNUNG
As mentioned above, the dianions of compounds 1 and 3
have already been reported. No information is yet available
ACHTUNGTRENNUNG
a
for a dianion that is derived from the bis
N
A
ACHTUNGTRENNUNG
(1,1-bis(diphenylphosphino)methane), but the monoanion
has been synthesized. Therefore, we reasoned that the
double deprotonation of compound 6 should be possible.
The synthesis of the neutral ligand was achieved in two
13C NMR spectrum, was identified as the central proton.
Confirmation of the successful monodeprotonation of com-
pound 6 was provided by X-ray diffraction analysis. Single
crystals of compound 6Li were grown by the diffusion of
pentane into a concentrated solution of 6Li in pyridine
(Figure 1). Compound 6Li crystallized as a dimer in the solid
state with two pyridine molecules acting as solvent for the
Li+ cations.
steps: DiphenylphosphinoACTHUNRGTNE(NUG methyl)diphenylphosphinesulfide
5 was synthesized according to a literature procedure[8] and
was further oxidized in situ to yield compound 6 in an over-
all yield of 70% (Scheme 2). In the 31P NMR spectrum,
Compared to neutral derivative 6, compound 6Li features
elongated PO and PS bond lengths (1.524(2) ꢂ and
Scheme 2. Synthesis of compound 6.
compound 6 exhibits an AB system at d=33.6 and 21.0 ppm
(2J
ACHTUNGTRENNUNG(P,P)=15 Hz). The central protons are found as a doublet
2
of doublet (2J
A
N
1
1
in the H NMR spectrum and at d=37.1 ppm (dd, J
45 Hz, JACHTUNGTRENNUNG
1
trum. To investigate the structural parameters of compound
6, single crystals were grown by the slow evaporation of a
concentrated solution of compound 6 in CH2Cl2 (for details
of the structure of compound 6, see the Supporting Informa-
tion).[9] The bond lengths and angles in compound 6 are all
standard.
Next, the single deprotonation of compound 6 was at-
tempted (Scheme 3). The reaction of compound 6 with one
equivalent of an alkyl lithium reagent (MeLi, BuLi, tBuLi)
in toluene, THF, or Et2O led to a color change from color-
less to yellow, concomitant with an evolution of gas.
After 15 min (1 h in toluene), a pale-yellow solid precipi-
tated from the crude mixture. This new compound was iso-
Figure 1. ORTEP plot of compound 6Li; ellipsoids are set at 50% proba-
bility. Hydrogen atoms (except for H1 and H26) and the phenyl rings
(except for the ipso carbon atoms) on the P atoms have been omitted for
ꢀ
ꢀ
ꢀ
clarity. Selected bond lengths [ꢂ]: C1 P1 1.721(3), C1 P2 1.703(3), P1
ꢀ
ꢀ
ꢀ
ꢀ
S1 1.994(1), P2 O1 1.524(2), O1 Li1 1.951(5), O1 Li2 1.922(5), C26 P3
ꢀ
ꢀ
ꢀ
ꢀ
1.721(3), C26 P4 1.702(3), P3 S2 1.992(1), P4 O2 1.523(2), O2 Li1
ꢀ
1.910(5), O2 Li2 1.922(5).
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16137

N. Mꢀzailles et al.
1.994(1) ꢂ in compound 6Li versus 1.495(1) ꢂ and
1.949(1) ꢂ in compound 6 for the PO and PS bonds, respec-
tively). On the contrary, the two PC bond lengths are signifi-
cantly shorter (1.721(3) ꢂ and 1.703(3) ꢂ in compound 6Li
versus 1.819(2) ꢂ and 1.818(2) ꢂ in compound 6). Following
this result, we tried to synthesize dianion 6Li2 (Scheme 3) but
the synthesis was not successful when following literature
procedures.[1] After optimization of the reaction conditions,
two equivalents of n-butyllithium, together with two equiva-
lents of TMEDA (tetramethylethylenediamine), were used
in Et2O.[10] Compound 6Li2 precipitated from the reaction
mixture and was easily isolated in a very good 75% yield.
Compound 6Li2 showed very poor solubility in toluene, 1,2-
dimethoxyethane (DME), and Et2O and decomposed in
THF and pyridine, thus rendering its NMR characterization
difficult. Interestingly, despite its very low solubility, com-
pound 6Li2 could be recrystallized from a saturated solution
in benzene and was characterized by X-ray diffraction
(Figure 2).
1.535(1) ꢂ, respectively). This result is in line with previous
findings and has been rationalized by DFT calculations.[1i]
A
trapping experiment with D2O was carried out to confirm
the double deprotonation. The reaction of compound 6Li2
with an excess of D2O in Et2O yielded the doubly deuterat-
ed compound 2D2 after work up and purification. The
1H NMR spectrum of compound 2D2 showed the absence of
any signals at d=3.75 ppm in CH2Cl2, which was indicative
of quantitative deuteration. The difference in bond length
(0.5 ꢂ) between the PS and the PO bonds is particularly in-
teresting. Indeed, in carbene complexes of transition metals
ꢀ
that incorporate geminal dianions as ligands, the M C dis-
tance is, on average, 2.393 ꢂ (CCDC search on 57 struc-
tures). Therefore, 4-membered metallacycles that contain
the PO moiety should be much more strained than their PS
counterparts and, hence, confer specific reactivity on their
corresponding complexes. To verify our hypothesis, we stud-
ied the coordination of compound 6Li2 with a RuII center.
The reaction of compound 6Li2 with [RuCl
(PPh3)4] in tol-
troscopy
uene was carried out and followed by 31P NMR spec
N
ACHTUNGTRENNUNG
(Scheme 4). After 15 min, the spectrum showed the pres-
ence of free triphenylphosphine, as well as numerous unre-
solved peaks. After several hours, four well-defined peaks
were observed, each of which integrated to one phosphorus
atom (d=73.7, 64.1, 46.7, and 14.0 ppm) and the signal for
free triphenylphosphine integrated to two phosphorus
atoms. After purification, a new complex (7) was isolated
and characterized by multinuclear NMR spectroscopy.
Unlike what was observed with the symmetrical
[(PPh2S)2CLi2] dianion, complex 7 was not the expected
1
ruthenium carbene.[11] Indeed, its H NMR spectrum showed
a multiplet at d=1.41 ppm, which corresponded to a proton
ꢀ ꢀ
on the P C P bridge.
Moreover, four separate signals at d=6.92, 6.65, 6.28, and
6.06 ppm were observed for the four aromatic protons that
were located on the same phenyl ring (determined by
COSY) at high field for aromatic protons. These patterns
are reminiscent of a RuII complex that was synthesized in
Figure 2. ORTEP plot of compound 6Li2; ellipsoids are set at 50% proba-
bility. Hydrogen atoms and solvent molecules have been omitted for
ꢀ
our group that resulted from the C H activation of a phenyl
ꢀ
ꢀ
ꢀ
clarity. Selected bond lengths [ꢂ]: C1 P1 1.671(2), C1 P2 1.681(2), P1
ring on the ligand.[2d] X-ray diffraction analysis confirmed
this hypothesis. Single crystals of compound 7 were grown
by the slow diffusion of pentane into a concentrated solution
in CH2Cl2 (Figure 3).
ꢀ
ꢀ
ꢀ
ꢀ
O1 1.535(1), P2 S1 2.0418(6), C1 Li1 2.189(3), C1 Li1’ 2.425(3), O1
ꢀ
Li1’ 1.928(3), S2 Li1 2.599(3).
In the solid state, compound
6Li2 crystallizes as a dimer; two
molecules of TMEDA com-
plete the coordination sphere
of the external lithium atoms
and three benzene molecules
(not shown). The geometrical
changes that were observed in
compound 6Li are more pro-
nounced in compound 6Li2. The
PC bonds are even shorter
(1.671(2) ꢂ and 1.681(2) ꢂ)
and the PS and PO bonds are
longer
(2.0418(6) ꢂ
and
Scheme 4. Synthesis of complexes 7 and 8.
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Mixed (P=S/P=O)-Stabilized Geminal Dianion
FULL PAPER
of complex 8 was ascertained by X-ray diffraction analysis
(Figure 4).[14] Its structure resembles that of complex 7,
ꢀ
except that the C H activation took place on a phenyl ring
of the PPh2S moiety. All of the bond lengths and angles in
Figure 3. ORTEP plot of complex 7; ellipsoids are set at 50% probability.
Hydrogen atoms (except for H1) and the phenyl rings of the PPh3 sub-
stituents (except for the ipso carbon atoms) have been omitted for clarity.
ꢀ
ꢀ
Selected bond lengths [ꢂ] and angles [8]: C1 P1 1.762(5), C1 P2
ꢀ
ꢀ
ꢀ
ꢀ
1.816(5), P1 S1 2.000(2), P2 O1 1.526(4), Ru1 C1 2.267(5), Ru1 S1
ꢀ
ꢀ
ꢀ
ꢀ
2.580(1), Ru1 O1 2.319(3), Ru1 C21 2.067(5), P2 C20 1.769(5), C20
ꢀ
ꢀ
ꢀ
ꢀ
C21 1.407(7), Ru1 P3 2.330(1), Ru1 P4 2.271(1); P1 C1 P2 116.6(3),
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
C1 Ru1 P4 160.5(1), S1 Ru1 C21 162.8(1), P4 Ru1 O1 162.5(1).
Figure 4. ORTEP plot of complex 8; ellipsoids are set at 50% probability.
Hydrogen atoms (except for H1) and the phenyl rings of the PPh3 sub-
stituents (except for the ipso carbon atoms) have been omitted for clarity.
ꢀ
ꢀ
Selected bond lengths [ꢂ] and angles [8]: C1 P1 1.80(1), C1 P2 1.80(2),
ꢀ
Indeed, complex 7 resulted from a C H activation of the
ꢀ
ꢀ
ꢀ
ꢀ
P1 S1 2.002(4), P2 O1 1.513(7), Ru1 C1 2.28(1), Ru1 S1 2.499(2),
ꢀ
ligand, which constitutes a formal C H addition to the Ru=
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Ru1 O1 2.428(7), Ru1 C9 2.04(1), P1 C8 1.75(2), C8 C9 1.43(1); P1
C1 P2 122.0(6), P3 Ru1 C1 160.5(3), C9 Ru1 O1 158.8(3), P4 Ru1
S1 168.4(1).
C bond. Such behavior has already been reported with simi-
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
lar ligands by the group of Cavell and by ourselves.[2c,d,12]
ꢀ
The Ru1 C21 distance (2.067(5) ꢂ) is much shorter than
ꢀ
the Ru1 C1 distance (2.267(5) ꢂ) and falls within the range
of other reported orthometalated ruthenium(II) com-
complex 8 are comparable to those in compound 7. Com-
pound 8 features disordered phenyl rings on the triphenyl-
plexes.[13] The C20 C21 distance (1.407(7) ꢂ) is longer than
the other C C bonds in the orthometalated phenyl ring. The
ꢀ
ꢀ
phosphine substituents. Here, again, one pair of dia
isomers is observed (RR/SS). Interestingly, the dia
selectivity is opposite to that observed for complex 7.
DFT calculations were carried out to rationalize the dia-
ACHTUNGTRENNUNG
ruthenium atom adopts a distorted octahedral geometry.
One phenyl ring on the PPh2O moiety is now orthometalat-
ed and the aromatic proton is now located on the central
carbon atom. Two triphenylphosphine ligands remain on the
metal center. Interestingly, only one pair of diastereoisomers
is observed by 31P NMR spectroscopy (SR/RS couple). In an
attempt to explore the reactivity of complex 7, a solution of
compound 7 was heated at 1108C in toluene. The reaction
mixture turned progressively from dark green to orange.
After heating for 12 h, the 31P NMR spectrum showed the
complete conversion of compound 3 into a new complex
that was characterized by an NMR pattern that was very
similar to that of complex 7 (note that no free triphenyl-
phosphine was observed during the process). Indeed, four
distinct signals, each of which integrated to one phosphorus
atom, were observed at d=53.4, 47.0, 45.4, and ꢀ12.8 ppm,
respectively. After evaporation of the solvent, complex 8
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
stereoselectivity and reversibility of this process. For this
purpose, we used the full model of compounds 7 and 8
(named VII and VIII, respectively). The calculations were
performed by using the Gaussian 03 set of programs[15] with
the b3pw91 functional[16] in combination with the 6-31G*
basis set for the metal-bound atoms (P, S, C, O), 6-31G for
the other atoms (C, H) in the orthometalated phenyl ring, 6-
311+ +G** for the migrating H atom, and STO-3G for all
other atoms (C, H).[17] The LANL2DZ basis set was used
for the Ru atoms, with an additional f-polarization function
(for full details on the theoretical calculations, see the Sup-
porting Information).[18,19] Because of our experimental ob-
ꢀ
servations, four C H activation pathways were computed.
Thus, our proposed mechanism for the transformation is:
1) Decoordination of the X atom (X=O, S) by rotation of
the P=X arm; 2) insertion of ruthenium into the aromatic
1
was isolated. Its H NMR spectrum also showed the pres-
ence of a central proton on the P C P bridge (d=
1.51 ppm), as well as four high-field signals that were attrib-
uted to an orthometalated phenyl ring. The exact structure
ꢀ ꢀ
ꢀ
C H bond; 3) hydrogen transfer from the ruthenium center
to the central carbon atom; 4) recoordination of the X atom
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16139

N. Mꢀzailles et al.
to the ruthenium center. The key step in determining the se-
lectivity of the process is the formation of the ruthenium–
hydride intermediate. Indeed, insertion of the ruthenium
transformation that occurs at room temperature. From the
ꢀ
unsaturated complex (VIIa), the C H insertion is very
facile, with a TS that is a mere 1.5 kcalmolꢀ1 higher in
energy, thus leading to Ru–carbene–hydride complex VIIb,
in which the H and O atoms are in opposite planes. The for-
mation of the ruthenium–alkyl species (VIIc) is then the
most favorable step (DG=ꢀ23.1 kcalmolꢀ1), again with a
ꢀ
atom into the C H bond can occur in two ways: In the first
case, both the heteroatom (O, S) and the hydride are in the
ꢀ ꢀ ꢀ
same plane (defined by the Ru C P Y atoms), whereas, in
the second case, they are in opposite planes.
¼
very low activation energy (DG =1.3 kcalmolꢀ1). It has
Formation of complex 7: The calculated mechanism and the
energy diagram for the formation of compound 7 are pre-
sented in Scheme 5 and Scheme 6, respectively.
The overall transformation is exergonic with a total DG=
ꢀ21.2 kcalmolꢀ1. The first step (decoordination of the phos-
phine oxide moiety) is the rate-determining step, with a cal-
culated barrier of 15.3 kcalmolꢀ1. This barrier, which is
much smaller than the related decoordination of PS (see
above), as expected from the ring strain, is consistent with a
been shown that hydride–carbene complexes and alkyl com-
plexes could be found in equilibrium through an a-H-trans-
fer reaction.[20] Here, the formation of alkyl complex VIIc is
highly favorable, thereby resulting in the sole formation of
the alkyl complex. Finally, recoordination of the O atom
takes place to yield the final ruthenium(II) product. The al-
ꢀ
ternative C H insertion was also calculated; the correspond-
ing intermediate, complex VIIb’, in which the hydrogen
atom is located in the same plane as the oxygen atom, is
3.3 kcalmolꢀ1 higher in energy than complex VIIb. More-
over, the final product (VIId’), which results from complex
VIIb’, was calculated to be about 15 kcalmolꢀ1 higher in
energy than complex VIId. Because those two complexes
are higher in energy than complexes VIIb and VIId, even if
the path were energetically accessible, only the formation of
the most stable complex (VIIb) would be possible. These
first calculations clearly explain why the starting carbene
complex is not observed in solution at room temperature,
because it rapidly evolves into complex 7. Moreover, the
calculations show that the energy that is required for this
process to be reversible is 36.5 kcalmolꢀ1. Thus, they corrob-
orate the observation that transformation of complex 7 only
proceeds upon prolonged heating at reflux in toluene.
Scheme 5. Proposed mechanism for the formation of complex 7.
Formation of complex 8: The same method was applied to
model compound VIII. The
calculated mechanism is given
in Scheme 7 and the corre-
sponding energies are given in
Scheme 8. Here, also, the rate-
determining step in the mecha-
nism for the formation of com-
plex 8 is the decoordination of
the thiophosphinoyl ligand
(DG=29.4 kcalmolꢀ1).
This
decoordination cannot be ach-
ieved at room temperature,
but is compatible with a reac-
tion temperature of 1108C. As
mentioned above, this barrier
is much higher than the one
for the decoordination of the
PO moiety. The rest of the
mechanism is very much like
the previous one for complex
VII.
The overall process is exo-
thermic
(DG=ꢀ25.8 kcal
Scheme 6. Computed energies of the intermediates in the formation of complex 7.
molꢀ1). In this case, the rever-
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Mixed (P=S/P=O)-Stabilized Geminal Dianion
FULL PAPER
31P NMR spectrum showed the formation of several uniden-
tified products, as well as some unreacted starting material.
The reaction with complex 8 was much more clear cut and
complete conversion of the starting complex into a single
new product (complex 9, Scheme 9), as characterized by
Scheme 9. Synthesis of complex 9.
Scheme 7. Proposed mechanism for the formation of complex 8.
four signals in the 31P NMR spectrum (d=52.2, 47.5, 30.5,
7.3 ppm), was observed within 30 min. 13C NMR analysis
confirmed the coordination of CO to the metal center: a
highly coupled signal was observed at d=206.8 ppm (which
sibility is unachievable because the reverse process would
require an activation energy of 55.2 kcalmolꢀ1. Complex
VIIId is about 4 kcalmolꢀ1 lower in energy than complex
VIId, which rationalizes the fact that only one product is ob-
tained in each case (at low or high temperature). These cal-
culations confirm our initial hypothesis of the higher reactiv-
ity of the phosphine oxide moiety compared to the thiophos-
phinoyl moiety (decoordination energy of 15.3 kcalmolꢀ1
for PO versus 29.4 kcalmolꢀ1 for PS). This higher reactivity
was further confirmed by reacting compounds 7 and 8 with
carbon monoxide. The reactions were performed in an
NMR tube that was plugged with a CO balloon. The reac-
tion of compound 7 with CO was not clean and the
ACTHNUTRGNEUNG
was seen as a singlet in the 13C{31P} NMR spectrum). The
exact structure of compound 9 was determined by X-ray dif-
fraction analysis. Single crystals of compound 9 were grown
by the slow diffusion of pentane into a concentrated solution
in CH2Cl2 (Figure 5).
As expected, the phosphine oxide moiety has been re-
placed by one molecule of CO in the coordination sphere of
the metal, trans to the orthometalated carbon atom. The
metal center still adopts a distorted octahedral geometry.
ꢀ
The Ru1 C1 distance is shortened by the coordination of
the CO molecule (2.260(2) ꢂ
in
compound
9
versus
2.28(1) ꢂ in compound 8).
Conclusion
In conclusion, we have devel-
oped an easy and efficient syn-
thesis of a new type of unsym-
metrical geminal dianion that
contains both
a
phosphine
oxide moiety and a thiophos-
phinoyl moiety. Coordination
to a RuII center showed that
the expected carbene complex
was not formed. Rather, the
weaker coordination of the P=
O arm, because of ring strain,
resulted in a hemilabile behav-
ior at room temperature. Fol-
lowing the decoordination of
ꢀ
the P=O arm, a facile C H ac-
tivation on a phenyl ring of
the ligand occurred in a dia-
stereospecific fashion. The re-
versibility of this process could
Scheme 8. Computed energies of the intermediates in the formation of complex 8.
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16141

N. Mꢀzailles et al.
9 mL, 14.4 mmol) at ꢀ788C. The reaction mixture was left to warm to
RT and stirred overnight. The resulting dark-red solution was transferred
with a cannular into a solution of Ph2PCl (2.65 mL, 14.4 mmol) in THF
(10 mL) at 08C. The reaction was left to stir for 4 h and H2O2 (35 wt.%
in H2O, 1.4 mL, 14.4 mmol) was added at 08C. Stirring for 3 h prompted
the precipitation of compound 6 as a white solid that was extracted by fil-
tration, washed with THF (2ꢃ10 mL) and Et2O (3ꢃ15 mL), and dried
under vacuum (4 g, 9.25 mmol, 64%). 1H NMR (300.0 MHz, CD2Cl2):
d=7.96–7.88 (m, 4H; Hortho Ph2PS), 7.77–7.63 (m, 4H; Hortho Ph2PO),
7.54–7.37 (m, 12H; Harom), 3.75 ppm (dd, 2J
14.5 Hz, 2H; PCH2P); 13C NMR (75.5 MHz, CD2Cl2): d=133.7 (dd, J-
(P,C)=2.6 Hz, J(P,C)=104 Hz; Cipso), 133.1 (dd, J(P,C)=1.5 Hz, J(P,C)=
84 Hz; Cispo), 132.0 (m, 8C; CHarom), 131.1 (m, 4C; CHarom), 128.7 (m,
(P,H)=12.4 Hz, 2J
ACHUTGTNRNEUNG ACHTUNGTRENNUNG(P,H)=
A
E
N
ACHTUNGTRENNUNG
8C; CHarom), 37.1 ppm (dd, 1J(P,C)=45 Hz, 1J
ACTHNUGTRENNUGN ACHTUNGTRENNNUG
31P NMR (121.5 MHz, CD2Cl2): d=33.6 (d, 2J
A
2
21.0 ppm (d, J
N
Synthesis of compound 6Li: To a suspension of compound 6 (139.3 mg,
0.32 mmol) in Et2O (5 mL) was added n-butyllithium (1.6m, 0.2 mL,
0.32 mmol) at ꢀ788C. The solution turned yellow and was left to warm
to RT and stirred for 1 h. A yellow solid precipitated that was extracted,
washed with Et2O (2ꢃ3 mL), and dried (120 mg, 85%). 1H NMR
(300.0 MHz, C6D5N): d=8.24–8.17 (m, 10H; Harom), 8.13–8.07 (m, 5H;
Figure 5. ORTEP plot of complex 9; ellipsoids are set at 50% probability.
Hydrogen atoms (except for H1) have been omitted for clarity. Selected
Harom), 8.03–7.96 (m, 5H; Harom), 2.33 ppm (br d, J
PC(H)P); 13C NMR (75.5 MHz, C6D5N): d=144.0 (dd, 3J
(P,C)=80 Hz; Cipso), 142.8 (dd, 3J(P,C)=6 Hz, 1J
(P,C)=100 Hz; Cipso),
132.5 (d, J(P,C)=10 Hz; CHarom), 131.8 (d, J(P,C)=10 Hz; CHarom), 130.0
(d, J(P,C)=3 Hz; CHpara), 129.7 (d, J(P,C)=3 Hz; CHpara), 128.3 (d, J-
(P,C)=10 Hz; CHarom), 128.2 (d, J(P,C)=10 Hz; CHarom), 23.5 ppm (dd,
1J(P,C)=105 Hz, 1J(P,C)=135 Hz; PCHP); 31P NMR (121.5 MHz,
C6D5N): d=35.3 (d, 2J(P,P)=24 Hz; PS), 33.8 ppm (d, 2J
(P,P)=24 Hz;
(C5H5N)2: C 71.09,
ACHTUNGTRENNUNG
ꢀ
ꢀ
ꢀ
bond lengths [ꢂ] and angles [8]: C1 P1 1.766(2), C1 P2 1.789(2), P1 S1
AHCTUNGTRENNUNG
ꢀ
ꢀ
ꢀ
ꢀ
2.0063(7), P2 O1 1.487(1), Ru1 C1 2.260(2), Ru1 C9 2.172(2), Ru1 C62
A
R
ACHTUNGTRENNUNG
ꢀ
ꢀ
ꢀ
ꢀ
1.900(2), Ru1 S1 2.5149(5), Ru1 P3 2.3524(5), Ru1 P4 2.3842(5), P1 C8
1.784(2), C62 O2 1.149(2), C8 C9 1.412(2); P1 C1 P2 125.9(1), C1
Ru1 P4 162.38(5), C9 Ru1 C62 175.85(7), Ru1 C62 O2 176.6(2), S1
A
ACHTUNGTRENNUNG
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
A
ACHTUNGTRENNUNG
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
A
ACHTUNGTRENNUNG
ꢀ
Ru1 P3 164.88(2).
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
PO); elemental analysis calcd (%) for C30H26LiNOP2S·CAHTUNGTRENNNUG
H 5.37, N 6.22; found: C 69.80, H 5.23, N 6.45.
be thermally promoted with this kinetic complex. A second
Synthesis of compound 6Li2: To a suspension of compound 6 (1.0 g,
2.32 mmol) in Et2O (10 mL) was added TMEDA (0.4 mL, 2.66 mmol).
At ꢀ788C, n-butyllithium (1.6m, 3 mL, 4.8 mmol) was added and the sol-
ution turned dark orange. After 1 h, compound 6Li2 precipitated as a
bright-yellow solid and the reaction was stirred for a further 2 h. Com-
pound 6Li2 was isolated by centrifugation, washed with Et2O (2ꢃ5 mL)
and pentane (2ꢃ8 mL), and dried (960 mg, 1.74 mmol, 75%). Elemental
analysis calcd (%) for C62H72Li4N4O2P4S2: C 66.43, H 6.47, N 5.00; found:
C 66.31, H 6.51, N 4.87.
ꢀ
diastereospecific C H activation was then observed, thereby
leading to the thermodynamic complex. These experimental
findings were fully rationalized by DFT calculations. An in-
vestigation of the reactivities of both the kinetic and the
thermodynamic complexes is currently underway in our lab-
oratory.
Synthesis of compound 6D2: To a suspension of compound 6Li2 (100 mg,
0.18 mmol) in Et2O (4 mL) was added D2O (40 mL, 2 mmol). An instant
color change from yellow to white was observed and the reaction was left
to stir for 2 h. The addition of CH2Cl2, filtration, drying over MgSO4, and
evaporation of the solvents afforded compound 6D2 as a white solid
(77 mg, 98%). 1H NMR (300.0 MHz, [D8]THF): d=7.93–7.85 (m, 4H;
Experimental Section
All reactions were performed under an inert atmosphere of argon or ni-
trogen by using Schlenk and glovebox techniques and dry deoxygenated
solvents. Dry Et2O, CH2Cl2, toluene, petroleum ether, and THF were ob-
tained by using a MBRAUN SPS-800 purifying system. NMR spectra
H
arom), 7.68–7.61 (m, 4H; Harom), 7.48–7.35 ppm (m, 12H; Harom);
13C NMR (75.5 MHz, [D8]THF): d=133.6 (dd, 3J(P,C)=2.7 Hz, 1J
(P,C)=
(P,C)=84 Hz; Cipso), 132.1 (d,
(P,C)=11 Hz; CHarom), 131.8 (d, J-
(P,C)=11 Hz; CHarom), 128.7 (pseudo-t,
(P,C)=24 Hz; 2ꢃCHarom), 36.6 ppm (m; PCD2P); 31P NMR
(121.5 MHz, [D8]THF): d=33.6 (d, 2J
(P,P)=14.5 Hz; PS), 21.0 ppm (d,
2J
(P,P)=14.5 Hz; PO).
Synthesis of complex 7: To a suspension of compound 6Li2 (100 mg,
0.18 mmol) in toluene (6 mL) was added [RuCl2A(PPh3)4] (220 mg,
A
ACHTUNGTRENNUNG
3
1
were recorded on
a Bruker AC-300 SY spectrometer operating at
104 Hz; Cipso), 133.1 (dd, J
(P,C)=3 Hz; CHpara), 131.9 (d, J
(P,C)=3 Hz; CHpara), 131.1 (d, J
SJ
ACHUTGTNREN(NUG P,C)=1.5 Hz, JACHTNUGTRENNUNG
300.0 MHz for 1H, 75.5 MHz for 13C, and 121.5 MHz for 31P nuclei. Sol-
vent peaks were used as an internal reference relative to SiMe4 for 1H
and 13C chemical shifts; 31P chemical shifts are reported relative to an ex-
ternal reference (85% H3PO4). Coupling constants are given in Hz. The
following abbreviations are used: s: singlet, d: doublet, dd: doublet of
doublet, br d: broad doublet, t: triplet, dt: doublet of triplets, m: multip-
J
A
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
let, br: broad signal. [RuCl2ACHTNUTRGNEG(UN PPh3)4] was prepared according to a litera-
CTHUNGTRENNUNG
ture procedure.[21] TMEDA was heated at reflux for 2 h over KOH and
distilled. Triphenylphosphine sulfide was obtained by the sulfuration of
triphenyl phosphine with elemental sulfur in THF. All other reagents and
chemicals were obtained commercially and used as received.
0.18 mmol). The solution was left to stir at RT for 3 h and turned dark
green. Centrifugation allowed the elimination of LiCl and the remaining
supernatant was dried under vacuum. Washing with petroleum ether (3ꢃ
5 mL) and drying under vacuum allowed the isolation of complex 7 as a
green powder (160 mg, 84%). 1H NMR (300.0 MHz, CD2Cl2): d=7.57–
7.50 (m, 6H; H of phenyl), 7.42–7.11 (m, 28H; H of phenyl), 7.06–8.97
(m, 7H; H of phenyl), 6.92 (1H; Ha), 6.83–6.77 (m, 5H; H of phenyl),
6.65 (m, 1H; Hb), 6.28 (m, 1H; Hc), 6.06 (m, 1H; Hd), 1.41 ppm (m, 1H;
CCDC-893613 (6), CCDC-893614 (6Li), CCDC-893615 (6Li2), CCDC-
893616 (7), CCDC-893617 (8), and CCDC-893618 (9) contain the supple-
mentary crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
PC(H)P); 13C NMR (75.5 MHz, CD2Cl2): d=145.0 (dd, J
(P,C)=15 Hz; Cd), 137.6 (d, J(P,C)=43 Hz; C of phenyl), 136.9 (d, J-
(P,C)=34 Hz; C of phenyl), 135.7 (d, J(P,C)=10 Hz; CH of phenyl),
ACHTUNGTREN(NUNG P,C)=2 Hz, J-
Synthesis of compound 6: To a solution of triphenylphosphinesulfide
(4.23 g, 14.4 mmol) in THF (20 mL) was added methyllithium (1.6m,
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
16142
www.chemeurj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 16136 – 16144

Mixed (P=S/P=O)-Stabilized Geminal Dianion
FULL PAPER
134.8 (m, CH of phenyl), 134.5 (br d, J
of phenyl), 132.2 (br s; CH of phenyl), 131.5 (d, J
phenyl), 130.8 (d, J(P,C)=10 Hz; CH of phenyl), 130.7 (d, J
10 Hz; CH of phenyl), 130.5 (d, J(P,C)=10 Hz; CH of phenyl), 130.4 (d,
(P,C)=11 Hz; CH of phenyl), 128.9 (br s; CH of phenyl), 128.8 (br s;
CH of phenyl), 128.6 (br s; CH of phenyl), 128.0 (br s; CH of phenyl),
127.9 (d, J(P,C)=11 Hz; CH of phenyl), 127.7 (d, J(P,C)=3 Hz; CH of
phenyl), 127.7 (d, J(P,C)=11 Hz; CH of phenyl), 127.5 (d, J(P,C)=
11 Hz; CH of phenyl), 125.2 (d, J(P,C)=3 Hz; Cc), 119.5 (d, J(P,C)=
15 Hz; Cb), 7.7 ppm (m; PC(H)P); 31P NMR (121.5 MHz, CD2Cl2): d=
73.7 (d, J(P,P)=27 Hz; 1P), 64.1 (d, J(P,P)=6 Hz; 1P), 46.7 ppm (m;
ACHTUNGTRENNUNG
[1] a) A. Kasani, R. P. K. Babu, R. McDonald, R. G. Cavell, Angew.
Chem. 1999, 111, 1580–1582; Angew. Chem. Int. Ed. 1999, 38, 1483–
1484; b) C. M. Ong, D. W. Stephan, J. Am. Chem. Soc. 1999, 121,
2939–2940; c) T. Cantat, N. Mꢀzailles, L. Ricard, Y. Jean, P. Le
Floch, Angew. Chem. 2004, 116, 6542–6545; Angew. Chem. Int. Ed.
2004, 43, 6382–6385; d) M. Demange, L. Boubekeur, A. Auffrant,
N. Mꢀzailles, L. Ricard, X. Le Goff, P. Le Floch, New J. Chem. 2006,
30, 1745–1754; e) K. L. Hull, B. C. Noll, K. W. Henderson, Organo-
metallics 2006, 25, 4072–4074; f) T. Cantat, L. Ricard, P. Le Floch,
N. Mezailles, Organometallics 2006, 25, 4965–4976; g) K. L. Hull, I.
Carmichael, B. C. Noll, K. W. Henderson, Chem. Eur. J. 2008, 14,
3939–3953; h) L. Orzechowski, G. Jansen, S. Harder, Angew. Chem.
2009, 121, 3883–3887; Angew. Chem. Int. Ed. 2009, 48, 3825–3829;
i) J.-H. Chen, J. Guo, Y. Li, C.-W. So, Organometallics 2009, 28,
4617–4620; j) O. J. Cooper, A. J. Wooles, J. McMaster, W. Lewis,
A. J. Blake, S. T. Liddle, Angew. Chem. 2010, 122, 5702–5705;
Angew. Chem. Int. Ed. 2010, 49, 5570–5573; k) P. Schrçter, V. Gess-
ner, Chem. Eur. J. 2012, 18, 11223–11227.
[2] a) R. G. Cavell, R. P. K. Babu, A. Kasani, R. McDonald, J. Am.
Chem. Soc. 1999, 121, 5805–5806; b) A. Kasani, R. McDonald,
R. G. Cavell, Chem. Commun. 1999, 1993–1994; c) N. D. Jones, G.
Lin, R. A. Gossage, R. McDonald, R. G. Cavell, Organometallics
2003, 22, 2832–2841; d) T. Cantat, M. Demange, N. Mꢀzailles, L.
Ricard, Y. Jean, P. Le Floch, Organometallics 2005, 24, 4838–4841;
e) T. Cantat, L. Ricard, N. Mꢀzailles, P. Le Floch, Organometallics
2006, 25, 6030–6038; f) T. Cantat, X. Jacques, L. Ricard, X. F.
Le Goff, N. Mꢀzailles, P. Le Floch, Angew. Chem. 2007, 119, 6051–
6054; Angew. Chem. Int. Ed. 2007, 46, 5947–5950; g) H. Heuclin, D.
Grꢄnstein, X.-F. Le Goff, P. Le Floch, N. Mꢀzailles, Dalton Trans.
2010, 39, 492–499; h) H. Heuclin, T. Cantat, X. F. Le Goff, P. Le
Floch, N. Mꢀzailles, Eur. J. Inorg. Chem. 2011, 2540–2546.
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
JACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
R
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
1P), 14 (m; 1P); elemental analysis calcd (%) for C61H50OP4RuS:
C 69.36, H 4.77; found: C 69.42, H 5.01.
Synthesis of complex 8: To a suspension of compound 6Li2 (100 mg,
0.18 mmol) in toluene was added [RuCl2ACTHNUTRGNEU(NG PPh3)4] (220 mg, 0.18 mmol).
The solution was left to stir at 1108C overnight, during which time it
turned orange. Centrifugation allowed the elimination of LiCl and the re-
maining supernatant was dried under vacuum. Washing with petroleum
ether (3ꢃ5 mL) and further drying under vacuum allowed the isolation
of complex 8 as a yellow powder (170 mg, 89%). 1H NMR (300.0 MHz,
CD2Cl2): d=7.73 (m, 5H; H of phenyl), 7.43–6.78 (m, 41H; H of
phenyl), 6.37 (ddd, J
Ha), 6.25 (m; Hb), 5.63 (m; Hc), 4.81 (m; Hd), 1.51 ppm (m; PC(H)P);
13C NMR (75.5 MHz, CD2Cl2): d=175.9 (m; RuC), 153.0 (br d, J
(P,C)=
108 Hz; Ph2P(S)C), 144.6 (dd, J(P,C)=2.4 Hz, J(P,C)=15 Hz; Cd), 139.7
(d, J(P,C)=35 Hz; C of phenyl), 139.2 (br s; C of phenyl), 139.1 (br s; C
of phenyl), 136.9 (dd, J(P,C)=10 Hz, J(P,C)=95 Hz; C of phenyl), 136.9
(dd, J(P,C)=4 Hz, J(P,C)=40 Hz; C of phenyl), 134.8 (d, J(P,C)=5 Hz;
CH of phenyl), 134.4 (d, J(P,C)=10 Hz; CH of phenyl), 131.3 (d, J-
(P,C)=3 Hz; CH of phenyl), 131.1 (d, J(P,C)=3 Hz; CH of phenyl),
130.9 (d, J(P,C)=11 Hz; CH of phenyl), 130.6 (d, J(P,C)=11 Hz; CH of
phenyl), 129.9 (d, J(P,C)=3 Hz; CH of phenyl), 129.3 (d, J(P,C)=11 Hz;
CH of phenyl), 128.7–128.2 (m; CH of phenyl), 127.7 (d, J(P,C)=10 Hz;
CH of phenyl), 127.4 (d, J(P,C)=10 Hz; CH of phenyl), 127.3 (d, J-
(P,C)=11 Hz; CH of phenyl), 126.0 (d, J(P,C)=16 Hz; Ca), 123.9 (d, J-
(P,C)=4 Hz; Cc), 118.1 (d, J(P,C)=15 Hz; Cb), 15.0 ppm (m; PC(H)P);
31P NMR (121.5 MHz, CD2Cl2): d=53.4 (dd,
(P,P)=6.6 Hz, (P,P)=
24 Hz; PPh3), 47.0 (dt, J(P,P)=10 Hz, J(P,P)=24 Hz; PPPh3), 45.4 (m;
P(O)), ꢀ12.8 ppm (m; P(S)).
ACHTUNGTRENNUNG(H,H)=1.5 Hz, JAHCTUNRTGEGUNN(N H,H)=7.3 Hz, JACHTGUNTREN(NUNG P,H)=12.5 Hz;
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
[3] a) C. Foo, K.-C. Lau, Y.-F. Yanga, C.-W. So, Chem. Commun. 2009,
6816–6818; b) G. Ma, M. J. Ferguson, R. G. Cavell, Chem.
Commun. 2010, 46, 5370–5372; c) R. Thirumoorthi, T. Chivers, I.
Vargas-Baca, Dalton Trans. 2011, 40, 8086–8088.
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Floch, Chem. Commun. 2005, 5178–5180; b) T. Cantat, F. Jaroschik,
L. Ricard, P. Le Floch, F. Nief, N. Mꢀzailles, Organometallics 2006,
25, 1329–1332.
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
J
N
JACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
Synthesis of complex 9: To a solution of complex 8 (50 mg) in CD2Cl2
(0.6 mL) was added CO (balloon). The solution turned from orange to
yellow. Complete conversion was determined by 31P NMR spectroscopy
and the mixture was evaporated to dryness (50 mg, 98%). 1H NMR
(300.0 MHz, CD2Cl2): d=7.78–6.95 (m, H; H of phenyl+Ha), 6.64 (m,
1H; Hb), 5.96 (m, 1H; Hc), 5.8 (m, 1H; Hd), 2.05 ppm (m, 1H; PC(H)P);
13C NMR (75.5 MHz, CD2Cl2): d=206.8 (m; CO), 183.5 (m; RuC), 148.0
(m; C of phenyl), 144.0 (m; CHd), {138.4, 137.8, 136.4} (C of phenyl),
[5] M. Fustier, X. F. Le Goff, P. Le Floch, N. Mꢀzailles, J. Am. Chem.
Soc. 2010, 132, 13108–13110.
[6] a) T. Cantat, T. Arliguie, A. Noꢅl, P. Thuꢀry, M. Ephritikhine, P. Le
Floch, N. Mꢀzailles, J. Am. Chem. Soc. 2009, 131, 963–972; b) O. J.
Cooper, J. McMaster, W. Lewis, A. J. Blake, S. T. Liddle, Dalton
Trans. 2010, 39, 5074–5076; c) J.-C. Tourneux, J.-C. Berthet, P.
Thuꢀry, N. Mꢀzailles, P. Le Floch, M. Ephritikhine, Dalton Trans.
2010, 39, 2494–2496; d) O. J. Cooper, D. P. Mills, J. McMaster, F.
Moro, E. S. Davies, W. Lewis, A. J. Blake, S. T. Liddle, Angew.
Chem. 2011, 123, 2431–2434; Angew. Chem. Int. Ed. 2011, 50, 2383–
2386; e) G. Ma, M. J. Ferguson, R. McDonald, R. G. Cavell, Inorg.
Chem. 2011, 50, 6500–6508; f) D. P. Mills, F. Moro, J. McMaster, J.
van Slageren, W. Lewis, A. J. Blake, S. T. Liddle, Nat. Chem. 2011, 3,
454–460; g) W. Ren, X. Deng, G. Zi, D.-C. Fang, Dalton Trans.
2011, 40, 9662–9664; h) J.-C. Tourneux, J.-C. Berthet, T. Cantat, P.
Thuꢀry, N. Mꢀzailles, P. Le Floch, M. Ephritikhine, Organometallics
2011, 30, 2957–2971; i) J.-C. Tourneux, J.-C. Berthet, T. Cantat, P.
Thuꢀry, N. Mꢀzailles, M. Ephritikhine, J. Am. Chem. Soc. 2011, 133,
6162–6165; j) D. P. Mills, O. J. Cooper, F. Tuna, E. J. L. McInnes,
E. S. Davies, J. McMaster, F. Moro, W. Lewis, A. J. Blake, S. T.
Liddle, J. Am. Chem. Soc. 2012, 134, 10047–10054.
132.5 (d, J
phenyl), 131.8 (d, J
CH of phenyl), 130.6 (br s; CH of phenyl), 129.9 (br s; CH of phenyl),
129.8 (br s; CH of phenyl), 128.8 (d, J(P,C)=10 Hz; CH of phenyl), 128.7
(d, J(P,C)=10 Hz; CH of phenyl), 128.1 (br s; CH of phenyl), 128.0 (d, J-
(P,C)=2 Hz; CH of phenyl), 127.8 (d, J(P,C)=2 Hz; CH of phenyl),
127.4 (br d, J(P,P)=8 Hz; CH of phenyl), 127.2 (d, J(P,C)=11 Hz; CH of
phenyl), 126.4 (d, J(P,C)=20 Hz; CHa), 125.0 (d, J(P,C)=3 Hz; CHc),
121.4 (d,
(P,C)=13 Hz; CHb), 24.6 ppm (m; PC(H)P); 31P NMR
(121.5 MHz, CD2Cl2): d=52.2 (dd, J(P,P)=8 Hz, J(P,P)=21 Hz; PPh3),
47.5 (dt, J(P,P)=6 Hz, J(P,P)=21 Hz; PPh3), 30.5 (d, J(P,P)=6 Hz; PO),
7.6 ppm (t, (P,P)=8 Hz; PS); elemental analysis calcd (%) for
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
C62H50O2P4RuS: C 68.68, H 4.65; found: C 68.40, H 4.61.
[7] a) R. G. Cavell, R. P. K. Babu, A. Kasani, J. Organomet. Chem.
2001, 617–618, 158–159; b) N. D. Jones, R. G. Cavell, J. Organomet.
Chem. 2005, 690, 5485–5496; c) T. Cantat, N. Mꢀzailles, A. Auffrant,
P. Le Floch, Dalton Trans. 2008, 1957–1972; d) H. Heuclin, M. Fust-
ier, A. Auffrant, N. Mꢀzailles, Lett. Org. Chem. 2010, 7, 596–611;
e) S. T. Liddle, D. P. Mills, A. J. Wooles, Chem. Soc. Rev. 2011, 40,
2164–2176.
Acknowledgements
The authors thank the CNRS (Centre National pour la Recherche Scien-
tifique) and the Ecole Polytechnique for financial support. H.H. is thank-
ful to the Ecole Polytechnique for a graduate fellowship.
Chem. Eur. J. 2012, 18, 16136 – 16144
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
16143

N. Mꢀzailles et al.
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group P212121; a=8.661(1), b=11.153(1), c=22.508(1) ꢂ; a=90.00,
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m=0.361 cmꢀ1
;
FACHTUNGTRENNUNG(000)=904; T=150.0(1) K; qmax =25.028; hkl
ranges: ꢀ9 to 10, ꢀ12 to 10, ꢀ26 to 15; 6071 reflections collected;
3430 unique reflections (Rint =0.0234); 3323 reflections with I>
2s(I); 263 parameters refined; GOF=1.056; R1=0.0310 and wR2=
0.0694; difference peak/hole (eꢂꢀ3) 0.264
G
ACHTUNGTRENN(UNG 0.040).
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Received: July 26, 2012
Published online: November 7, 2012
16144
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