A new mixed P,S-bidentate ligand featuring a λ4- phosphinine anion and a phosphanyl sulfide group - Synthesis, x-ray crystal structures and catalytic properties of its chloro(cymene)ruthenium and allylpalladium complexes

Article abstract of DOI:10.1002/ejic.200400555

1,3,2-Diazaphosphinine (1) reacts successively with diphenylacetylene and diphenyl(1-propynyl)phosphane sulfide to afford the P,S-bidentate phosphinine 3. Reaction of nBuLi with 3 followed by complexation with [RuCl₂(C ₁₀H₁₄)]₂ gave two diastereoisomers 5a,b. Variable-temperature NMR spectroscopy and ONIOM DFT calculations were carried out to rationalize their formation. Complexes 5a,b were used as catalysts in hydrogen-transfer hydrogenation (TON up to 200). Reaction of MeLi with 3 followed by complexation with [PdCl₂(η³-C ₃H₅)]₂ yielded two diastereomers 7a,b, which were used as catalysts in the Suzuki-Miyaura cross-coupling reaction of aryl bromides with pinacolborane to yield the corresponding arylboronic esters (TON up to 799000). Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400555

FULL PAPER
A New Mixed P,S-Bidentate Ligand Featuring a λ4-Phosphinine Anion and a
Phosphanyl Sulfide Group ؊ Synthesis, X-ray Crystal Structures and Catalytic
Properties of Its Chloro(cymene)ruthenium and Allylpalladium Complexes
Maximilian Dochnahl,[a] Marjolaine Doux,[a] Emilie Faillard,[a] Louis Ricard,[a] and
Pascal Le Floch*[a]
Keywords: Density functional calculations / Homogeneous catalysis / P ligands / Ruthenium / Palladium / S ligands
1,3,2-Diazaphosphinine (1) reacts successively with di-
phenylacetylene and diphenyl(1-propynyl)phosphane sulf-
200). Reaction of MeLi with 3 followed by complexation with
[PdCl2(η3-C3H5)]2 yielded two diastereomers 7a,b, which
ide to afford the P,S-bidentate phosphinine 3. Reaction of were used as catalysts in the Suzuki−Miyaura cross-coupling
nBuLi with 3 followed by complexation with [RuCl2(C10H14)]2
gave two diastereoisomers 5a,b. Variable-temperature NMR
spectroscopy and ONIOM DFT calculations were carried out
to rationalize their formation. Complexes 5a,b were used as
catalysts in hydrogen-transfer hydrogenation (TON up to
reaction of aryl bromides with pinacolborane to yield the cor-
responding arylboronic esters (TON up to 799000).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
Introduction
These tridentate ligands, which are readily available from
the reaction of nucleophiles with phosphinines, were found
to exhibit very specific electronic properties. Thus, their
rhodium(i) complexes show a high reactivity towards small
molecules such as O2, CO2, CS2 and SO2.[13] Furthermore,
their palladium(ii) complexes proved to be active catalysts
in the Miyaura cross-coupling reaction that allows the syn-
thesis of arylboronic esters from pinacolborane and haloar-
enes.[14]
Since the pioneering work of Grim and co-workers in
the mid-1970s,[1] there has been a continuing interest in the
chemistry of mixed tertiary phosphane/monochalcogenide
(λ3,σ3)PϪX (X ϭ O, S) ligands.[2Ϫ7] These systems, which
combine soft σ-donor (P) and good π-donor (O, S) binding
sites, display very unique steric and electronic properties
that differ markedly from those of classical bidentate phos-
phorus ligands. Most importantly, in some cases, these com-
pounds have been employed to build very active catalysts.
For example, in 1995 it was shown that a rhodium(i) com-
plex of the monosulfide of dppm (dppm ϭ Ph2PCH2PPh2)
could efficiently catalyze the carbonylation of methanol.[8]
Later on, palladium(ii) complexes of the same ligands were
shown to be active catalysts for the ethylene/CO copolymer-
ization.[9] On the other hand, P,O-mixed ligands, such as
monoxides of dppm and dppe (Ph2PCH2CH2PPh2) and
dppp (Ph2PCH2CH2CH2PPh2), give better results than
classical bidentate phosphanes in the cobalt-catalyzed
hydroformylation of epoxides due to their hemilability.[10]
In 2002 we reported the synthesis of a new type of S,P,S-
pincer ligand that incorporates a pseudo-ylidic λ4-phos-
phorus atom as the central binding site (Scheme 1).[11,12]
Scheme 1
Exploiting the same strategy, Yoshifuji et al. reported this
year on the synthesis of mixed P,S-systems of the type
(RPϭCϪPϭS) featuring a kinetically stabilized phosphaal-
kene (λ3,σ2-phosphorus atom) and a phosphane sulfide
group.[15,16] A cationic palladium(ii) complex of these new
low-coordinate, phosphorus-based ligands was employed as
a catalyst in the direct conversion of allyl alcohol to allyl-
aniline.[17]
Initially, we postulated that the presence of two ancillary
phosphane sulfide groups was a prerequisite for the stabiliz-
ation of these new types of σ complexes. Indeed, it is well-
known that 1-alkylphosphininyllithium salts usually react
[a]
´ ´ ´ ´
Laboratoire ‘‘Heteroelements et Coordination’’, UMR CNRS
´
7653 (DCPH), Departement de Chimie, Ecole Polytechnique,
´
92128 Palaiseau Cedex, France
Fax: ϩ 33-1-69333990
E-mail: lefloch@poly.polytechnique.fr
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2005, 125Ϫ134
DOI: 10.1002/ejic.200400555
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
125

M. Dochnahl, M. Doux, E. Faillard, L. Ricard, P. Le Floch
FULL PAPER
through their π-system with metal fragments to yield the
corresponding η5-coordinated complexes.[18Ϫ23] In this arti-
cle, we show that anionic bidentate P,S-ligands featuring a
pseudo-ylidic λ4-phosphorus atom can be easily assembled
from a diphenyl(2-phosphininyl)phosphane sulfide.
Results and Discussion
The synthetic strategy used for the synthesis of these new
systems relies on the reactivity of 4,6-di-tert-butyl-1,3,2-di-
azaphosphinine (1) towards functionalised alkynes.[24,25]
This precursor proved to be a very efficient source of tetra-
functionalised phosphinines through successive [4 ϩ 2]
cycloaddition/cycloreversion processes with functionalised
alkynes. We first focused our work on the synthesis of di-
phenyl(3-R-5,6-diphenylphosphinin-2-yl)phosphane sulfide
derivatives. Azaphosphinine 2, which was only used as a
transient species, was readily formed by warming equimolar 0.8
amounts of 1 and diphenylacetylene at 60 °C in toluene for
3 d (Scheme 2).
Figure 1. ORTEP view of a molecule of ligand 3; ellipsoids are
scaled to enclose 50% of the electron density; the numbering is
arbitrary and different from that used in the assignment of the
˚
NMR spectra; selected distances [A] and bond angles [°]: P1ϪC1
1.739(2), C1ϪC2 1.406(2), C2ϪC3 1.395(2), C3ϪC4 1.392(2),
C4ϪC5 1.404(2), C5ϪP1 1.736(2), C1ϪP2 1.824(2), P2ϪS1
1.954(1); P1ϪC1ϪC2 124.4(1), C1ϪC2ϪC3 120.8(2), C2ϪC3ϪC4
126.6(2), C3ϪC4ϪC5 121.7(2), C4ϪC5ϪP1 123.9(1), C5ϪP1ϪC1
102.60(7),
P1ϪC1ϪP2
115.1(1);
(mean
plane
C1ϪC2ϪC4ϪC5)ϪP1 0.45, (mean plane C1ϪC2ϪC4ϪC5)ϪC3
As previously explained, the synthesis of the correspond-
ing 1-alkylphosphininyllithium salts can be conventionally
achieved by treating equimolar amounts of phosphinines
with nucleophiles. Thus, 3 was treated with n-butyllithium
in THF at Ϫ78 °C to afford the lithium salt 4, which was
identified by 31P NMR spectroscopy. The lithium salt 4 ap-
pears as an AB system [δ ϭ Ϫ37.6 (PϪBu) and 42.4 ppm
Scheme 2
2
(PPh2) in THF at 25 °C; JP,P ϭ 151.9 Hz]. The chemical
Compound 2 proved to be sufficiently reactive to un-
dergo a second [4 ϩ 2] cycloaddition/cycloreversion process
with 1 equiv. of alkynyl-substituted diphenylphosphane sul-
fides in toluene at reflux. We chose MeϪCϵCϪP(S)Ph2 for
this reaction in order to increase the solubility of the ligand.
We found that the reaction with diphenyl(1-propynyl)phos-
shift of the ring phosphorus atom (δ ϭ Ϫ37.6 ppm) is simi-
lar to those of other 1-alkylphosphininyllithium salts.[14,23]
Reaction of 4 with the dimer [Ru(η6-C10H14)Cl2]2 was
carried out in THF at low temperature. After warming to
room temperature, the 31P NMR spectrum of the crude
mixture indicated that two complexes 5a and 5b had formed
in a 3:1 ratio (Scheme 4).
phane sulfide only yielded phosphinine 3, which was iso-
lated as an air-stable, white solid and was fully charac-
terized by NMR techniques and elemental analysis. The
presence of the diphenylphosphane sulfide group at the α-
position of the phosphorus atom was evidenced in the 31P
2
NMR spectrum by a large JP,P coupling constant of
108.2 Hz (in CDCl3 at 25 °C) (Scheme 3). The formulation
proposed on the basis of NMR spectroscopic data was con-
firmed by an X-ray crystal structure analysis. A view of
a molecule of 3 is presented in Figure 1; crystal data are
summarized in the Exp. Sect. This structure deserves no
particular comments as the metric parameters fall in the
usual range for λ3-phosphinines.
Scheme 4
Both complexes appear as an AB spin-system with close
chemical shifts (δ ϭ 40.7 and 44.3 ppm for 5a and δ ϭ 43.4
2
and 45.9 ppm for 5b) and JP,P coupling constants
(115.5 Hz for 5a and 97.2 Hz for 5b). The only major differ-
Scheme 3
ence between 5a and 5b in the 1H NMR spectra arises from
126
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Eur. J. Inorg. Chem. 2005, 125Ϫ134

A New Mixed P,S-Bidentate Ligand
FULL PAPER
˚
the chemical shifts of the aromatic protons of the cymene [2.4239(5) A] falls in the usual range of PϭSϪRu bond
ligand: in 5a two hydrogen signals are shifted to high field lengths.[27,28] As previously noted in the structures of Ni,
3
(doublets at δ ϭ 3.17 and 3.69 ppm with JH,H ϭ 5.5 and Pd, Pt and Rh complexes,[12,13] the phosphorus atom and
6.1 Hz, respectively) compared with those of 5b (doublets the C3 carbon atom lie out of the plane defined by the C1,
3
at δ ϭ 4.13 and 4.17 ppm with JH,H ϭ 6.0 and 5.6 Hz, C2, C4 and C5 atoms by 12.6° and 1.8°, respectively, to
respectively) and other reported complexes.[26] Fortunately, yield a boat-like conformation. The phosphorus atom is
complex 5a proved to be insoluble in diethyl ether, thus al- now pyramidal (sum of angles at P1 ϭ 313.8°) and com-
lowing the separation of the two diastereomers. Single crys- pares well with classical tertiary phosphanes.
tals of complex 5a were obtained at room temperature from
Additional experiments were carried out in order to see
C6D6 as solvent (crystals deposited during the recording of which factors control the ratio between 5a and 5b. However,
the NMR spectra). An ORTEP view of a molecule of 5a is whatever the experimental conditions used (concentration
presented in Figure 2; crystal data are presented in the Exp. and reaction temperature) the 3:1 ratio initially obtained
Sect. As can be seen, the complex adopts a classical piano- could not be significantly modified. Variable-temperature
stool structure with the n-butyl substituent at the phos- NMR experiments were also carried out on the mixture of
phorus atom pointing backwards probably to avoid steric 5a and 5b but, even under reflux in THF, no interconver-
congestion with the cymene ligand. The most interesting sion could be observed. The stereochemistry of 5a could
finding is related to the external PϪC and PϭS bond not be established on the sole basis of its NMR spectro-
lengths. The shortening of the C1ϪP2 bond from 1.824(2) scopic data. In theory, four diastereomers can be formed
˚
in 3 to 1.745(2) A in 5a and the elongation of the P2ϭS1 (5a,b,c,d; Scheme 5) depending on the orientation of the
˚
bond from 1.954(1) in 3 to 2.0283(7) A in 5a suggests a substituent at the phosphorus atom (backwards in 5a and
slight delocalization over the P1ϪC1ϪP2ϪS1ϪRu1 skel- 5b, inwards in 5c and 5d) and on the orientation of the
eton. This induces a relocalization of the internal PϪC and methyl and isopropyl groups of the cymene ligand. Al-
CϪC bonds within the phosphinine ring: for instance, though simple molecular modelling strongly suggests that
˚
C2ϪC3 and C4ϪC5 shorten [1.372(3) and 1.376(3) A, diastereomers 5c and 5d could not be formed because of
respectively] with respect to the free ligand [1.395(2) and the important steric congestion between the cymene ligand
˚
1.404(2) A] whereas C1ϪC2, C3ϪC4 and C5ϪP1 lengthen and both the substituent at the phosphorus atom and one
˚
[1.422(3), 1.435(2) and 1.805(2) A in 5a compared with of the phenyl groups of the diphenylphosphane sulfide
˚
1.404(2), 1.394(2) and 1.736(2) A in 3]. The SϪRu bond group, the four diastereomers were computed using the
ONIOM method at the B3LYP/UFF level (see Exp. Sect.
for details on basis sets and partition of the molecule into
QM and MM shells). In these calculations the n-butyl
group at the phosphorus atom was replaced by a methyl
group to minimize the degrees of freedom. Optimizations
of the theoretical complexes 5c and 5d failed and no min-
ima could be located, the ligand being displaced away from
the RuϪCl fragment during the optimization. The intro-
duction of an n-butyl group at the phosphorus atom would
not yield a different result due to the bulkiness generated
by the alkyl chain. However, two minima could be located
for structures Ia (model of 5a) and Ib (model of 5b). Two
views of these theoretical structures are presented in Fig-
Figure 2. ORTEP view of a molecule of complex 5a; ellipsoids are
scaled to enclose 50% of the electron density; the numbering is
arbitrary and different from that used in the assignment of the
˚
NMR spectra; selected distances [A] and bond angles [°]: P1ϪC1
1.790(2), C1ϪC2 1.422(3), C2ϪC3 1.372(3), C3ϪC4 1.435(2),
C4ϪC5 1.376(3), C5ϪP1 1.805(2), P1ϪBu 1.852(2), C1ϪP2
1.745(2), P2ϪS1 2.0283(7), Ru1ϪP1 2.3351(5), Ru1ϪS1 2.4239(5),
Ru1ϪCl1 2.4186(5), Ru1ϪC35 2.237(2), Ru1ϪC36 2.239(2),
Ru1ϪC37 2.196(2), Ru1ϪC38 2.276(2), Ru1ϪC39 2.257(2),
Ru1ϪC40 2.189(2), Ru1ϪCt 1.725, C35ϪC36 1.442(3), C36ϪC37
1.401(3), C37ϪC38 1.420(3), C38ϪC39 1.408(3), C39ϪC40
1.430(3), C40ϪC35 1.402(3); P1ϪC1ϪC2 121.1(1), C1ϪC2ϪC3
122.5(2), C2ϪC3ϪC4 125.3(2), C3ϪC4ϪC5 125.1(2), C4ϪC5ϪP1
119.2(1), C5ϪP1ϪC1 102.82(8), P1ϪC1ϪP2 111.9(1); (mean plane
C1ϪC2ϪC4ϪC5)ϪP1 12.55, (mean plane C1ϪC2ϪC4ϪC5)ϪC3
1.75
Scheme 5
Eur. J. Inorg. Chem. 2005, 125Ϫ134
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
127

M. Dochnahl, M. Doux, E. Faillard, L. Ricard, P. Le Floch
FULL PAPER
˚
Table 1. Selected bond lengths [A] for calculated structures Ia,b
Ia
Ib
P1ϪC2
C2ϪC3
C3ϪC4
C4ϪC6
C6ϪC7
C7ϪP1
P1ϪR8
C26ϪC2
C37ϪC3
C48ϪC6
C7ϪP12
P12ϪS13
P1ϪRu14
S13ϪRu14
Cl15ϪRu14
C16ϪRu14
C17ϪRu14
C18ϪRu14
C19ϪRu14
C20ϪRu14
C21ϪRu14
C74-cycle
C78-cycle
C79ϪC78
C80ϪC78
1.812
1.388
1.440
1.386
1.429
1.806
1.851
1.492
1.491
1.512
1.757
2.061
2.385
2.449
2.443
2.328
2.391
2.385
2.228
2.327
2.321
1.499
1.517
1.531
1.536
1.810
1.387
1.439
1.386
1.431
1.814
1.851
1.491
1.491
1.513
1.759
2.059
2.391
2.432
3.329
2.407
2.357
2.349
2.291
2.361
2.442
1.499
1.519
1.532
1.530
Single-point calculations at the B3LYP level of theory
carried out on both optimized ONIOM structures revealed
that the model complex Ia is more stable than the isomer Ib
(∆∆H ϭ Ϫ4.8 kcal/mol), thus confirming the experimental
results. Most importantly, no transition state could be lo-
cated between Ia and Ib, the rotation of the cymene ligand
around its centroidϪruthenium axis being completely
Figure 3. Optimized structures of model complexes Ia (a) and Ib
(b) obtained at the ONIOM(B3LYP/UFF) level of theory; atoms
included in the QM part are shown in ball-and-stick format and blocked by the two peripheral phenyl groups. This result
atoms included in the MM part are represented by tubes; the num-
bering is the same for Ia and Ib
allows us to rationalize why no interconversion between 5a
and 5b is observed, even under heating.
The catalytic activity of complexes 5a,b in the transfer
hydrogenation of ketones was tested (Scheme 6).[29Ϫ34] Re-
actions were conducted in 2-propanol as a proton source
and solvent and KOH as base using 0.5 mol % of catalysts
in most cases. The results are summarized in Table 2. As
can be seen, although conversion is acceptable, long reac-
tion times are needed to achieve complete conversions. It
must be noted that no efforts have been made, so far, to
improve these figures (solvents, role of the base, amount
of catalyst).
ure 3; fully labelled molecules of Ia,b are presented in the
Supporting Information. The most significant bond lengths
and bond angles of Ia,b are reported in Table 1. As can be
seen by examining these data, there is an acceptable fit be-
tween theoretical and experimental parameters. In Ia the
P,S-ligand and the RuϪCl, RuϪS and RuϪP bond lengths
are very close to those of the X-ray structure of 5a: for
instance, in Ia the P1ϪC2, C7ϪP12, P12ϪS13, Ru14ϪS13
and Ru14ϪP1 bond lengths are 1.812, 1.757, 2.061, 2.449
˚
and 2.385 A, respectively, versus 1.805, 1.745, 2.028, 2.424
˚
and 2.335 A in 5a. The only discrepancies arise in the cy-
mene ring. Despite excellent agreement between the CϪC
bond lengths (for example C19ϪC20, C74ϪC21, C78ϪC79
˚
are 1.407, 1.511 and 1.534 A, respectively, in Ia versus
1.401, 1.511 and 1.534 A in 5a), the cymene ring is too far
˚
Scheme 6
away from the ruthenium atom (the C16ϪRu14 distance is
2.328 A in Ia compared to 2.189 A in 5a). Modification of
The synthesis of a [Pd(η3-C3H5)]ϩ complex of the lithium
˚
˚
the basis set for Ru (all-electron basis sets rather than ECP) salt 4 was also investigated. As previously reported for the
was not performed due to the already long computational synthesis of 5a,b, reaction of phosphinine 3 with methyllith-
time. The same trends are observed between Ia and Ib and ium in THF at Ϫ78 °C afforded the lithium salt 6, which
deserve no other comment.
was identified by 31P NMR spectroscopy. Like 4, the lith-
128
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Eur. J. Inorg. Chem. 2005, 125Ϫ134

A New Mixed P,S-Bidentate Ligand
FULL PAPER
group and the phenyl group in the C6 position of the phos-
phinine ring. A similar phenomenon has already been re-
ported for other complexes.[35,36]
Table 2. Transfer hydrogenation of ketones using complex 5a,b as
catalyst; conditions: substrate (2 mmol), catalyst 5a,b (0.5 mol %,
unless stated otherwise), 10 mL of 0.1 m KOH in iPrOH, 80 °C,
2.5 d.
Crystals of 7a suitable for X-ray analysis were obtained
by slow diffusion of hexanes into a solution of complexes
7a,b in CDCl3. An ORTEP view of 7a is presented in Fig-
ure 4 and the refinement parameters are given in the Exp.
Sect. This structure confirms the η3-coordination of the al-
lyl moiety and also that the geometry around the palladium
Entry Substrate
Yield (%)[a] Time[b] TON
1
2
3
4
5
6
9
10
11
12
13
14
4-heptanone
1,3-diphenylacetone
cyclohexanone
2,6-dimethylcyclohexanone
acetophenone
acetophenone
91.6
100
2.5
2.5
2.5
2.5
0.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
183.2
200
200
200
82.1
195.2
100
100
˚
atom is trigonal-planar. The P1ϪPd [2.2778(6) A] and the
82.1[c]
˚
S1ϪPd [2.3371(6) A] bond lengths are similar to classical
97.6
96.6
100
94.1
98.5
4-Br-acetophenone
4-F-acetophenone
4-methyl-acetophenone
benzophenone
193.2 phosphaneϪpalladium and PϭSϪPd bond lengths,[36] al-
200
182.8
197
90.1
200
though the P1ϪPd distance is greater than in previously
reported tridentate palladium complexes.[12] The PdϪC32,
˚
PdϪC33, PdϪC34 [2.138(3), 2.137(3), 2.199(3) A] and
4,4Ј-dimethoxy-benzophenone 72.1[d]
˚
C32ϪC33 and C33ϪC34 [1.359(4) and 1.383(5) A] bond
transchalcone
100
lengths and the C32ϪC33ϪC34 angle [123.8(3)°] are in the
typical range of η3-allylpalladium complexes.[37Ϫ40] The ge-
ometry of the phosphinine moiety is similar to that in com-
plex 5a and deserves no further comment. In the major iso-
mer an H,C-HSQC NMR experiment showed that the sig-
nals of the two hydrogen atoms of the CH2 allyl fragments
at δ ϭ 2.16 and 2.52 ppm are connected, as are those at
δ ϭ 3.00 and 4.21 ppm. An H,H-NOESY experiment also
revealed that, in this same isomer, the PϪMe group (C6 in
the ORTEP view) is in the spatial neighbourhood of only
two hydrogen atoms of the CH2 allyl fragments (at δ ϭ 2.16
and 2.52 ppm) and is far from the CH and the other CH2
fragments (at δ ϭ 4.89, 3.00 and 4.21 ppm, respectively).
The major isomer is therefore complex 7a.
[a]
Yields were determined by 1H NMR spectroscopy, mass spec-
[b]
[c]
[d]
trometry or GC.
of catalyst.
In days.
1 mol % of catalyst.
0.8 mol %
ium salt 6 appears as an AB system with comparable chemi-
cal shifts [δ ϭ Ϫ40.7 (PϪMe) and 42.5 ppm (PPh2) in THF
at 25 °C; JP,P ϭ 156.7 Hz]. Reaction of 6 with the dimer
2
[Pd(η3-C3H5)Cl]2 was carried out in THF at low tempera-
ture. After warming to room temperature, the 31P NMR
spectrum of the crude mixture indicated that complexes 7a
and 7b had formed in a 3:1 ratio (Scheme 7). Complexes 7a
(major isomer) and 7b (minor isomer) appear as an AB
spin-system with very similar chemical shifts (δ ϭ 24.6 and
52.4 ppm for 7a and δ ϭ 23.4 and 52.0 ppm for 7b) and
2JP,P coupling constants (135.8 Hz for 7a and 132.7 Hz for
7b). Separation of complexes 7a and 7b could not be
achieved despite many attempts. These complexes were,
however, fully characterized by 1H and 13C NMR spec-
The catalytic activity of complexes 7a,b was tested in the
SuzukiϪMiyaura cross-coupling reaction, which allows the
synthesis of arylboronic esters from haloarenes and phenyl-
boronic acid (Scheme 8).[41Ϫ49] The reactions were conduc-
1
troscopy, and elemental analysis. In the H NMR spectrum
of 7, two sets of five non-equivalent η3-allyl proton reson-
ances are observed. One of the signals of the minor isomer
7b overlaps with those of the major isomer 7a.
Isomer interconversion was investigated by variable-tem-
perature NMR experiments but no conversion was ob-
served. We suppose that the rotation of the allyl moiety is
disfavoured by a repulsive interaction between the CH2 allyl
Figure 4. ORTEP view of one molecule of complex 7a; ellipsoids
are scaled to enclose 50% of the electron density; the numbering is
arbitrary and different from that used in the assignment of the
˚
NMR spectra; selected distances [A] and bond angles [°]: P1ϪC1
1.802(2); C1ϪC2 1.360(3), C2ϪC3 1.444(3), C3ϪC4 1.378(3),
C4ϪC5 1.422(3), C5ϪP1 1.756(2), P1ϪC6 1.828(2), C5ϪP2
1.733(2), P2ϪS1 2.0288(8), Pd1ϪP1 2.2778(6), PdϪS1 2.3371(6),
PdϪC32 2.138(3), PdϪC33 2.137(3), PdϪC34 2.199(3), C32ϪC33
1.359(4), C33ϪC34 1.383(5); P1ϪC1ϪC2 117.2(2), C1ϪC2ϪC3
123.4(2), C2ϪC3ϪC4 124.5(2), C3ϪC4ϪC5 121.0(2), C4ϪC5ϪP1
117.5(2),
C5ϪP1ϪC1
101.7(1),
P1ϪC5ϪP2
117.8(1),
C32ϪC33ϪC34 123.8(3); (mean plane C1ϪC2ϪC4ϪC5)ϪP1 21.7;
(mean plane C1ϪC2ϪC4ϪC5)ϪC3 7.3
Scheme 7
Eur. J. Inorg. Chem. 2005, 125Ϫ134
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129

M. Dochnahl, M. Doux, E. Faillard, L. Ricard, P. Le Floch
FULL PAPER
ted in toluene in the presence of K2CO3 using 0.0001 mol % Experimental Section
of catalyst in most cases. The results are summarized in
General Remarks: All reactions were routinely performed under ar-
Table 3. As can be seen, the conversions obtained in the
transformation of aryl bromides are acceptable: turnover
numbers (TONs) fall in the range of 242000 for electron-
rich arenes (4-bromoanisole) to 799000 for electron-de-
ficient species (4-bromoacetophenone). It must be noted
that no efforts were made to improve these results (solvents,
role of the base). However, under the same experimental
conditions (toluene at reflux), no reaction was observed
with the less-reactive aryl chlorides, even when using 2.0
mol % of catalyst.
gon or nitrogen with Schlenk and glove-box techniques and dry
deoxygenated solvents. Dry THF and hexanes were obtained by
distillation from Na/benzophenone, dry diethyl ether from CaCl2
and then NaH, and dry CH2Cl2 from P2O5. CDCl3 was dried with
˚
P2O5 and stored over Linde molecular sieves (4 A). C6D6 was used
as purchased and stored in the glovebox. [PdCl(C3H5)]2 was pur-
chased from Fluka. NMR spectra were recorded with a Bruker
Avance 300 spectrometer operating at 300.0 MHz for 1H,
75.5 MHz for 13C and 121.5 MHz for 31P. Solvent peaks are used
as internal reference relative to SiMe4 for 1H and 13C chemical
shifts (ppm); 31P chemical shifts are quoted relative to an 85%
H3PO4 external reference. Coupling constants are given in Hz.
Mass spectra were obtained at 70 eV with an HP 5989B spec-
trometer coupled to an HP 5980 chromatograph by the direct inlet
method. Elemental analyses were performed by the ‘‘Service d’ana-
lyse du CNRS’’, at Gif sur Yvette, France. Diazaphosphinine 1,[24]
[51]
diphenyl(1-propynyl)phosphane sulfide[50] and [RuCl2(η6-C10H14)]2
were prepared according to reported procedures.
Scheme 8
Phosphinine 3: Diphenylacetylene (3.79 g, 21 mmol) was added to
a solution of diazaphosphinine 1 in toluene (8 ϫ 10Ϫ5 mol/mL,
20 mmol) and the mixture was stirred at 60 °C for 72 h. Consump-
tion of 1 (δ ϭ 269.0 ppm) and formation of the 5,6-diphenyl-1,2-
azaphosphinine 2 (δ ϭ 267.4 ppm) was checked by 31P NMR spec-
troscopy.
Diphenyl(1-propynyl)phosphane
sulfide
(3.44 g,
22 mmol) (δ ϭ 18.8 ppm) was then added and the solution was
stirred at 120 °C for 96 h. After evaporation of the solvent, the
solid was washed with hexanes (3 ϫ 20 mL) and MeOH (20 mL)
and the resulting solid was dissolved in hot MeOH and stored at
0 °C. The white solid that separated was washed several times with
cold MeOH (3 ϫ 30 mL). After drying, 3 was recovered as a white
solid. Yield: 6.0 g (62%). Crystals suitable for X-ray crystallography
were obtained by slow diffusion of hexanes into a solution of 3 in
Table 3. SuzukiϪMiyaura reaction of aryl halides using complex 7
as catalyst; conditions: aryl bromide (1.0 mmol), phenylboronic
acid (1.5 mmol), K2CO3 (2.0 mmol) catalyst 7 (0.0001 mol % unless
stated otherwise), 10 mL of toluene, 110 °C, 24 h
Entry Substrate
Yield (%)[a] Benzene (%)[a] TON
1
2
3
4
5
bromobenzene
80.9[b]
50.0
43.2
5.6
5.4
8.6
9.8
9.4
80 900
500 000
432 000
244 000
799 000
1
CH2Cl2. H NMR (300 MHz, CDCl3, 25 °C): δ ϭ 2.67 (s, CH3),
bromobenzene
4-bromoanisole
4-bromotoluene
7.00Ϫ7.98 (m, 21 H, CH of Ph and H4) ppm. 13C NMR
3
(75.5 MHz, CDCl3, 25 °C): δ ϭ 25.4 (d, JC,P ϭ 8.2, CH3),
24.4
B
4-bromoacetophenone 79.9
127.2Ϫ133.5 (m, CH of Ph), 132.9 (dd, JC,P ϭ 84.6, JC,P ϭ 5.3,
B
A
3
3
C), 138.6 (vt, JC,P ϭ JC,P ϭ 12.8, C4H), 141.3 (s, C), 141.7 (s,
C), 148.0 (dd, JC,P ϭ 9.1, JCB ,P ϭ 3.8, C), 149.0 (dd, JC,P ϭ 12.8,
A
[a]
[b]
Yields were determined by GC. 0.01 mol % of catalyst.
JC,P ϭ 4.5, C), 1B59.4 (dd, JC,P ϭ 76.3, JC,P ϭ 67.2, C), 166.2
A
B
(dd,AJC,P ϭ 58.9, JC,P ϭ 14.3,B C) ppm. 31P ANMR (121.5 MHz,
B
A
2
CDCl3, 25 °C): δ ϭ 42.6 (d, JP ,P ϭ 108.1, PBPh2), 226.7 (d,
A
B
2JP ,P ϭ 108.1, PA) ppm. MS (CH2Cl2): m/z ϭ 479 [Mϩ], 447
[MAϪ S]ϩ, 416 [M Ϫ PS]. C30H24P2S (478.49): calcd. C 75.30, H
B
5.06; found C 74.97, H 4.72.
Conclusion
Lithium Salt 4: A solution of BuLi (0.235 mL, 1.6 m, 0.38 mmol)
was added through a syringe into a solution of 3 (180 mg,
0.38 mmol) in THF (6 mL) at Ϫ78 °C. The solution was warmed
to room temperature and stirred for 20 min. After evaporation of
the solvent, the solid was washed several times with hexanes (3 ϫ
2 mL). After drying, 4 was recovered as a red solid. Yield: 100%.31P
We have developed an access to a new class of ligands
that features a pseudo-ylidic phosphorus atom and a PϭS
ancillary arm. Interestingly, this allows to show that coordi-
nation through the phosphorus atom in 1-alkylphosphinin-
yllithium salts does not require the presence of two pendant
ancillary PϭS ligands. Although the catalytic activity of the
(cymene)Ru derivatives in the transfer hydrogenation of ke-
tones was found to be modest, interesting conversion yields
were obtained in the Pd-catalysed synthesis of arylboronic
esters from bromoarenes and phenylboronic acid. Further
studies are now focusing on the synthesis of other tran-
sition-metal complexes and investigation of their catalytic
properties.
2
NMR (121.5 MHz, THF, 25 °C): δ ϭ Ϫ37.6 (d, JP ,P ϭ 151.9,
A
B
2
PAϪBu), 42.4 (d, JP ,P ϭ 151.9, PBPh2).
A
B
Ruthenium Complexes 5a,b: A solution of BuLi (0.235 mL, 1.6 m,
0.38 mmol) was syringed into a solution of 3 (180 mg, 0.38 mmol)
in THF (6 mL) at Ϫ78 °C. The solution was warmed to room tem-
perature and stirred for 20 min. Complete formation of the lithium
salt 4 was checked by 31P NMR spectroscopy. In a glovebox,
[RuCl2(cymene)]2 (115 mg, 0.19 mmol) was added to the solution
and the solution was stirred for 1 h. After removing the solvent,
130
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Eur. J. Inorg. Chem. 2005, 125Ϫ134

A New Mixed P,S-Bidentate Ligand
FULL PAPER
the resulting solid was dissolved in toluene and filtered through
Celite. After drying, 5 was recovered as a red solid containing a
Lithium Salt 6: A solution of MeLi (0.235 mL, 1.6 m, 0.38 mmol)
was added through a syringe into a solution of 3 (180 mg,
mixture of two diastereoisomers (25:75). Yield: 242 mg (80%). The 0.38 mmol) in THF (6 mL) at Ϫ78 °C. The solution was warmed
major diastereoisomer, which is insoluble in diethyl ether, could be
obtained by washing the red solid several times with diethyl ether
(3 ϫ 10 mL). The resulting filtrate was kept at 0 °C overnight dur-
ing which time the minor diastereoisomer separated as a red solu-
tion.
to room temperature and stirred for 20 min. After evaporation of
the solvent, the solid was washed several times with hexanes (3 ϫ
2 mL). After drying, 6 was recovered as a red solid. Yield: 100%.31P
2
NMR (121.5 MHz, THF, 25 °C): δ ϭ Ϫ46.7 (d, JP ,P ϭ 156.7,
A
B
2
PAϪMe), 42.5 (d, JP ,P ϭ 156.7, PBPh2) ppm.
A
B
Major Diastereoisomer 5a: Yield: 150 mg (49%). Crystals suitable
for X-ray crystallography were deposited from a solution of 5a in
Palladium Complexes 7a,b: A solution of MeLi (0.156 mL, 1.6 m,
0.25 mmol) was added through a syringe into a solution of 3
(120 mg, 0.25 mmol) in THF (5 mL) at Ϫ78 °C. The solution was
3
C6D6. 1H NMR (300 MHz, C6D6, 25 °C): δ ϭ 0.97 (d, JH,H
ϭ
3
7.0, 3 H, CH3ϪCH of cymene), 0.97 (t, JH,H ϭ 7.2, 3 H, CH3 of warmed to room temperature and stirred for 20 min. Complete for-
nBu), 1.17 (d, JH,H ϭ 6.7, 3 H, CH3ϪCH of cymene), 1.50Ϫ1.58 mation of the lithium salt 6 was checked by 31P NMR spectroscopy.
3
(m, 2 H, CH2 of nBu), 1.72 (s, 3 H, CH3 of phosphinine), 1.95 (s,
In a glovebox, [PdCl(C3H5)]2 (44 mg, 0.12 mmol) was added to the
3 H, ArϪCH3 of cymene), 2.14Ϫ2.28 (m, 1 H, CH2 of nBu), solution and the mixture stirred for 1 h. After removing the solvent,
2.32Ϫ2.50 (m, 1 H, CH2 of nBu), 2.52Ϫ2.69 (m, 1 H, CH2 of nBu), the resulting solid was dissolved in CH2Cl2 and filtered through
2.99Ϫ3.09 (m, 2 H, ArϪCH of cymene and CH2 of nBu), 3.17 (d,
Celite. After drying, 7 was recovered as a brown solid containing a
3
3JH,H ϭ 5.5, ArϪH of cymene), 3.69 (d, JH,H ϭ 6.1, ArϪH of mixture of two diastereoisomers (25:75). No further purification
cymene), 4.67 (d, 3JH,H ϭ 6.1, ArϪH of cymene), 5.06 (d, 3JH,H ϭ
was carried out to separate the two diastereoisomers. Crystals of
7a suitable for X-ray diffraction were obtained by slow diffusion of
4
5.5, ArϪH of cymene), 5.43 (d, JH,P ϭ 6.3, H4), 6.88Ϫ7.12 (m,
12 H, H of Ph), 7.55Ϫ7.58 (m, 2 H, H of Ph), 7.69Ϫ7.80 (m, 4 H, hexane into a CH2Cl2 solution of 7a,b Yield: 123 mg (77%).
H of Ph), 7.88Ϫ7.95 (m, 2 H, H of Ph) ppm. 13C NMR
Major Diastereoisomer 7a: 1H NMR (300 MHz, CDCl3, 25 °C):
(75.5.5 MHz, C6D6, 25 °C): δ ϭ 13.2 (s, CH3 of nBu), 15.4 (s,
2
δ ϭ 1.19 (d, JH,P ϭ 8.1, 3 H, PAMe), 1.65 (s, 3 H, Me), 2.16 (d,
A
ArϪCH3 of cymene), 18.2 (s, CH3 of isopropyl), 22.9 (vt, ΣJC,P
ϭ
2JH,H ϭ 13.2, 1 H, CH2 allyl), 2.52 (d, 3JH,H ϭ 6.4, 1 H, CH2 allyl),
3
5.1, CH3 of isopropyl), 23.6 (d, JC,P ϭ 11.6, CH2 of nBu), 24.5
A
2
3
3.00 (dd, JH,H ϭ 13.2, JH,H ϭ 10.4, 1 H, CH2 allyl), 4.21 (vt,
2
(s, CH3 of phosphinine), 25.9 (d, JC,P ϭ 7.5, CH2 of nBu), 29.1
A
2JH,H ϭ JH,H ϭ 6.5, 1 H, CH2 allyl), 4.89 (m, CH allyl), 5.57 (d,
3
1
(s, CH of isopropyl), 42.5 (d, JC,P ϭ 19.8, PAϪCH2), 60.0 (dd,
A
4JH,P ϭ 5.9, H4), 7.04Ϫ8.09 (m, 20 H, H of Ph) ppm. 13C NMR
1JC,P ϭ 104.9, JC,P ϭ 55.9, C2), 67.5 (s, C of cymene), 75.1 (s,
1
A
A
B
1
3
(75.5.5 MHz, CDCl3, 25 °C): δ ϭ 17.1 (dd, JC,P ϭ 20.6, JC,P
ϭ
CH of cymene), 87.1 (s, CH of cymene), 89.1 (s, CH of cymene),
2.7, PAMe), 25.9 (dd, 3JC,P ϭ 4.2, 3JC,P ϭ 3.1, Me), 55.0 (dd, JC,P ϭ
111.7, JC,P ϭ 54.2, C2/6), 59.6 (d, 2JC,P ϭ 5.7, CH2 allyl), 69.1 (dd,
2JC,P ϭ 32.4, 4JC,P ϭ 4.5, CH2 allyl), 109.8 (dd, JC,P ϭ 47.9, JC,P ϭ
5.1, C2/6), 113.4 (dd, JC,P ϭ 12.6, JC,P ϭ 10.1, C4), 117.0 (d,
2JC,P ϭ 6.4, CH allyl), 125.1Ϫ133.1 (m, CH and C of Ph), 136.9
2
90.4 (d, JC,P ϭ 9.1, CH of cymene), 94.4 (s, C of cymene), 99.3
A
(dd, 1JC,P ϭ 43.8, 3JC,P ϭ 7.6, C6), 112.6 (dd, JC,P ϭ 12.8, JC,P ϭ
A
B
6.8, C4H), 114.8 (d, JC,P ϭ 9.1, C), 123.3Ϫ132.8 (m, CH of Ph),
134.1 (m, C), 134.7 (m, C), 141.8 (dd, JC,P ϭ 15.9, JC,P ϭ 2.3, C),
144.2 (d, JC,P ϭ 5.3, C3), 145.1 (d, JC,P ϭ 7.6, C5), 150.2 (d, JC,P ϭ
1.5, C) ppm. 31P NMR (121.5 MHz, C6D6, 25 °C): δ ϭ 40.7 (d,
(dd, JC,P ϭ 78.1, JC,P ϭ 7.2, C3/5), 143.5 (dd, JC,P ϭ 8.8, JC,P
ϭ
2.9, C3/5), 144.4 (d, JC,P ϭ 15.6, C of Ph), 145.4 (d, JC,P ϭ 1.9, C
2
2JP ,P ϭ 115.5, P), 44.3 (d, JP ,P ϭ 115.5, P) ppm.
A
B
A
B
of Ph) ppm. 31P NMR (121.5 MHz, CDCl3, 25 °C): δ ϭ 24.6 (d,
Minor Diastereoisomer 5b: Yield: 33 mg (11%). 1H NMR
(121.5 MHz, C6D6, 25 °C; selected data): δ ϭ 0.88Ϫ2.44 (m, 25 H,
Bu, iPr, 3 ϫ Me), 4.13 (d, 3JH,H ϭ 6.0, ArϪH of cymene), 4.17 (d,
2JP,P ϭ 135.8, PA), 52.4 (d, JP,P ϭ 135.8, PBPh2).
2
Minor Diastereoisomer 7b: 1H NMR (300 MHz, CDCl3, 25 °C):
δ ϭ 1.16 (br. s, 3 H, PMe), 1.65 (s, 3 H, Me), 1.72 (d, 2JH,H ϭ 13.3,
3
3JH,H ϭ 5.6, ArϪH of cymene), 4.91 (d, JH,H ϭ 6.0, ArϪH of
2
1 H, CH2 allyl), 2.90 (d, JH,H ϭ 13.4, 1 H, CH2 allyl), 3.18 (d,
3
4
cymene), 4.96 (d, JH,H ϭ 5.7, ArϪH of cymene), 5.31 (d, JH,P
ϭ
2JH,H ϭ 7.0, 1 H, CH2 allyl), 5.01 (m, 1 H, CH allyl), 7.04Ϫ8.09
(m, 20 H, H of Ph) ppm; signals of 1 H of CH2 allyl and H4 were
not observed. 13C NMR (75.5.5 MHz, CDCl3, 25 °C): δ ϭ 18.2
5.5, H4), 6.70Ϫ8.25 (m, 20 H, H of Ph) ppm. 31P NMR
2
(121.5 MHz, C6D6, 25 °C): δ ϭ 43.4 (d, JP ,P ϭ 97.2, P), 45.9 (d,
2JP ,P ϭ 97.2, P). C44H47ClP2RuS (806.34):Acalcd. C 65.54, H 5.87;
B
fouAnd C 65.22, H 5.48.
B
1
3
(dd, JC,P ϭ 20.0, JC,P ϭ 2.7, PAMe), 25.9 (m, Me), 55.0 (m, C2/
6), 59.1 (d, JC,P ϭ 5.1, CH2 allyl), 70.0 (m, CH2 allyl), 108.7 (m,
C2/6), 113.6 (dd, JC,P ϭ 12.8, JC,P ϭ 9.5, C4), 116.8 (d, JC,P
2
2
Hydrogenation of Ketones: A mixture of complexes 5a,b (8 mg,
ϭ
0.01 mmol, 0.5 mol %) was added to a solution of ketone (2 mmol, 6.3, CH allyl), 124.4Ϫ133.5 (m, CH and Cq of Ph), 136.2 (d, JC,P ϭ
1 equiv.) in KOH/2-propanol (0.1 m, 10 mL). The mixture was
stirred at 80 °C for 2.5 d. The progress of the reaction was moni-
tored by GC, mass spectrometry or 1H NMR spectroscopy. The
mixture was then neutralized with a saturated solution of 3 m HCl
(3 mL) and NaHCO3 (15 mL), and it was then extracted with di-
chloromethane (3 ϫ 15 mL). The organic layers were collected and
dried with MgSO4 and the solvents evaporated to yield the corre-
sponding alcohol. The alcohols were characterised by comparing
83.9, C3/5), 143.2 (dd, JC,P ϭ 11.7, JC,P ϭ 3.0, C3/5), 144.2 (d,
J
C,P ϭ 8.8, C of Ph), 145.7 (d, JC,P ϭ 2.1, C of Ph) ppm. 31P NMR
2
(121.5 MHz, CDCl3, 25 °C): δ ϭ 23.4 (d, JP,P ϭ 132.7, PϪMe),
52.0 (d, JP,P ϭ 132.7, PPh2) ppm. C34H32P2PdS (641.00): calcd. C
2
63.70, H 5.03; found C 63.46, H 4.81.
Suzuki؊Miyaura Reaction of Aryl Halides: Catalyst 7 as a toluene
solution (1.00 mL), made up to the correct concentration by mul-
tiple volumetric dilutions of a stock solution, was added to a mix-
ture of the aryl halide (1.0 mmol), PhB(OH)2 (0.183 g, 1.5 mmol)
and K2CO3 (0.276 g, 2.0 mmol) in toluene (10 mL). The resultant
mixture was then heated at 110 °C for 24 h, cooled and quenched
with HCl(aq) (2 m, 40 mL). The organic layer was removed and the
1
their H and 13C NMR spectra with reported NMR spectroscopic
data and by mass spectrometry.
Characterization of Secondary Alcohols: 4-Heptanol,[52] 1,3-di-
phenyl-2-propanol,[53] syn-2,5-dimethylcyclohexanol,[54] 1-phenyl-
ethanol,[55]
diphenylmethanol,[56]
1-(p-bromophenyl)ethanol,[57] aqueous layer was extracted with toluene (3 ϫ 50 mL). The com-
bis(p-methoxyphenyl)methanol.[58]
bined organic layers were washed with water, dried (MgSO4), fil-
Eur. J. Inorg. Chem. 2005, 125Ϫ134
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
131

M. Dochnahl, M. Doux, E. Faillard, L. Ricard, P. Le Floch
FULL PAPER
Table 4. Crystal data and structural refinement details for 3, 5a and 7a
3
5a
7a
Empirical formula
Mr
C30H24P2S
478.49
monoclinic
P21/c
6.611(5)
42.648(5)
17.464(5)
90
92.430(5)
90
4919(4)
8
1.292
0.278
C44H47ClP2RuS
806.34
monoclinic
P21/n
11.3830(10)
22.7280(10)
14.6770(10)
90
91.5450(10)
90
3795.7(5)
4
1.411
0.654
C34H32P2PdS
641.00
Crystal system
Space group
triclinic
¯
P1
˚
a [A]
11.2180(10)
12.0220(10)
12.7300(10)
67.8200(10)
77.4300(10)
69.3200(10)
1480.3(2)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
ρ [g cmϪ3
]
1.438
0.827
µ [cmϪ1
]
Crystal size [mm]
F(000)
Index ranges
0.20 ϫ 0.20 ϫ 0.20
2000
Ϫ8 Յ h Յ 8
Ϫ55 Յ k Յ 57
Ϫ23 Յ l Յ 23
28.70
597
16
22198
12430
9562
0.1143
0.18 ϫ 0.14 ϫ 0.10
1672
Ϫ16 Յ h Յ 16
Ϫ29 Յ k Յ 31
Ϫ20 Յ l Յ 20
30.03
447
18
18845
11031
8413
0.1046
0.22 ϫ 0.18 ϫ 0.05
656
Ϫ15 Յ h Յ 15
Ϫ16 Յ k Յ 15
Ϫ17 Յ l Յ 17
30.03
360
17
18500
8591
2Θmax [°]
Parameters refined
Data/parameters
Reflections collected
Independent reflections
Reflections used
wR2
6275
0.0790
R1
0.0414
1.054
0.0377
1.007
0.0344
1.018
Goodness of fit
Largest diff peak/hole [e·A
Ϫ3
˚
]
0.352(0.060)/Ϫ0.404(0.060)
0.983(0.084)/Ϫ0.932(0.084)
0.853(0.072)/Ϫ0.750(0.072)
tered and the solvent removed under reduced pressure. The residue LeeϪYangϪParr non-local correlation functional[67]) and the UFF
was dissolved in toluene (6 mL), hexadecane (0.068 m in CH2Cl2,
1.00 mL, internal standard) was added and the conversion into
product determined by GC.
force field[68] was used for the molecular mechanic calculations. In
all calculations (QM and QM/MM), the lanl2dz basis set was used
for the ruthenium atom.[69] The 6-31ϩG(d) basis set was used for
all atoms directly bound to the ruthenium centre (P, S, Cl atoms
as well as the C atoms of the aromatic part of the cymene ligand).
The C and H atoms of the phosphinine ring were calculated using
the 6-31G(d) basis set. Full optimizations were realized at the
ONIOM level, followed by analytical computation of the Hessian
matrix to confirm the nature of the located minima on the potential
energy surface. A single-point calculation was performed on the
ONIOM optimized structures at the B3LYP level of theory using
the 6-31G(d) basis sets for C, H, P, S, and Cl atoms and the lanl2dz
basis set for Ru.
Characterizations of Suzuki؊Miyaura Coupling Products: The
NMR spectra of the biphenyl compounds were compared with
those of commercial products (Aldrich); 4-methylbiphenyl,[59] 4-
methoxybiphenyl,[59] 4-acetylbiphenyl.[60]
X-ray Crystallographic Study: Crystals of 3 and 7a suitable for X-
ray diffraction were obtained by slow diffusion of hexane into a
CH2Cl2 solution of 3 and 7a. Crystals of 5a suitable for X-ray
diffraction deposited overnight from a solution in C6D6. Data were
collected at 150.0(1) K with a Nonius Kappa CCD diffractometer
˚
equipped with an Mo-Kα (λ ϭ 0.71070 A) X-ray source and a
Supporting Information: See footnote on the first page of this
article. Fully labelled structures of Ia and Ib and the geometrical
graphite monochromator, using ϕ and ω scans. The crystal struc-
tures were solved by using SIR 97[61] and SHELXL-97.[62] For parameters of the theoretical structures.
ORTEP drawings ORTEP III for Windows was used.[63] Further
details can be found in Table 4. CCDC-242764 to -242766 (for 3,
5a and 7a) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge at www.ccdc.cam.-
ac.uk/conts/retrieving.html [or from the Cambridge Crystallo-
Acknowledgments
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
Fax: ϩ 44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
This work was supported by the CNRS, the Ecole Polytechnique
and the DGA. M. D. thanks the DGA for financial support. The
authors would like to thank IDRIS (Paris XI Orsay University) for
the allocation of computer time.
Theoretical Mmethods: All calculations were performed with the
Gaussian 03 set of programs using the ONIOM method.[64] The
two complexes were optimized at the ONIOM(B3LYP/UFF)
level,[65] where the QM part was treated within the framework of
density functional theory at the B3LYP level (B3 for Becke’s
three-parameter exchange functional[66] and LYP for the
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