The CO/PC analogy in coordination chemistry and catalysis

Article abstract of DOI:10.1016/j.jorganchem.2004.09.066

This short account summarizes recent results obtained in the coordination chemistry of phosphinines and emphasizes their analogy with CO ligands. Reduced complexes can be easily assembled through the reaction of reduced 2,2′-biphosphinine dianions with transition metal fragments. Theoretical calculations were performed to establish the oxidation state of the metal in these complexes. Though many reduced complexes are available, phosphinines proved to be too sensitive toward nucleophiles to be used as efficient ligands in most catalytic processes. However, the high electrophilicity of the phosphorus atom can be exploited to synthesize phosphacylohexadienyl anions which exhibit a surprising coordination chemistry. When phosphino sulfide groups are incorporated as ancillary tridentate anionic SPS ligands can be easily produced. These ligands can bind different transition metal fragments such as M-X (M = group 10 metal, X = halogen), Rh-L (L = 2 electron donor ligand), Cu-X and Au-X (X = halogen). Palladium(II) complexes proved to be active catalyst in the Miyaura cross-coupling reaction. Bidentate anionic PS ligands were also synthesized following a similar approach. Their Pd(II) (allyl) derivatives showed a very good activity in the Suzuki catalyzed cross-coupling process that allows the synthesis of biphenyl derivatives through the reaction of phenylboronic acid with bromoarenes.

Full text of DOI:10.1016/j.jorganchem.2004.09.066

Journal of Organometallic Chemistry 690 (2005) 2407–2415
www.elsevier.com/locate/jorganchem
The CO/PC analogy in coordination chemistry and catalysis
Marjolaine Doux, Audrey Moores, Nicolas M e´ zailles, Louis Ricard,
Yves Jean, Pascal Le Floch *
Laboratoire ‘‘H e´ t e´ ro e´ l e´ ments et Coordination’’ UMR CNRS 7653, Ecole Polytechnique, 91128 Palaiseau Cedex, France
Received 29 September 2004; accepted 29 September 2004
Available online 6 November 2004
Abstract
This short account summarizes recent results obtained in the coordination chemistry of phosphinines and emphasizes their
0
analogy with CO ligands. Reduced complexes can be easily assembled through the reaction of reduced 2,2 -biphosphinine dian-
ions with transition metal fragments. Theoretical calculations were performed to establish the oxidation state of the metal in these
complexes. Though many reduced complexes are available, phosphinines proved to be too sensitive toward nucleophiles to be
used as efficient ligands in most catalytic processes. However, the high electrophilicity of the phosphorus atom can be exploited
to synthesize phosphacylohexadienyl anions which exhibit a surprising coordination chemistry. When phosphino sulfide groups
are incorporated as ancillary tridentate anionic SPS ligands can be easily produced. These ligands can bind different transition
metal fragments such as M–X (M = group 10 metal, X = halogen), Rh–L (L = 2 electron donor ligand), Cu–X and Au–X
(
X = halogen). Palladium(II) complexes proved to be active catalyst in the Miyaura cross-coupling reaction. Bidentate anionic
PS ligands were also synthesized following a similar approach. Their Pd(II) (allyl) derivatives showed a very good activity in
the Suzuki catalyzed cross-coupling process that allows the synthesis of biphenyl derivatives through the reaction of phenylbo-
ronic acid with bromoarenes.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Reduction; Catalysis; Complexes; Phosphorus heterocycles; Macrocycles
1
. Introduction
phosphines 1 or their Horner–Emmons equivalents 2
with aldehydes (Scheme 1) [2].
The ‘‘analogy’’ that exists between carbon and phos-
The coordinative abilities of doubly or triply bonded
systems also attracted a lot of attention since the discov-
ery of the first phosphametallocene by Mathey et al. [3]
in 1975. Since then, a considerable number of structures
involving p-cordination of P@C or P@C based systems
have been reported and the domain rapidly expanded
over the last ten years. Significant applications have also
emerged especially in the area of homogeneous catalysis
using complexes of aromatic phosphorus heterocycles
such as phospholide anions [4].
phorus in their low coordinated states slowly emerged as
a significant field of investigation in the modern chemis-
try of main group elements [1]. Though, this analogy is
limited, it clearly appears that molecules which feature
doubly and triply bonded carbon-phosphorus systems
behave as their carbon counterparts in some organic
transformations. Among numerous reactions, one of
the most illustrative examples is given by the phos-
pha-Wittig process that allows the formation of
phosphaalkenes from the reaction phosphoranyliden-
All these developments have found their origin in the
complementary nature of carbon and phosphorus. In-
deed, though at first sight phosphorus and carbon could
be considered as very different elements with regards to
*
Corresponding author. Tel.: +33 169 334570; fax: +33 169 333990.
E-mail address: lefloch@poly.polytechnique.fr (P.L. Floch).
0
022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.09.066

2408
M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
R1
oping the use of bi and polydentate ligands featuring
phosphinines as binding sites [8]. One of the most fa-
mous ligand to be reported in this series was the 2,2 -
biphosphinines 6 whose synthesis was achieved in 1991
R
P
P
0
R
M
R
1
1
R1
P
R CHO
H
or
[
9]. As expected from theoretical and electrochemical
data, these bidentate ligands markedly differ from their
R1
M
R2
OR
M
0
P
P
nitrogen counterparts, the ubiquitous 2,2 -bipyridines.
0
OR
O
Whereas 2,2 -bipyridine are well adapted to the coordi-
0
2
nation of electron-deficient metal centers, 2,2 -biphos-
1
: M = W(CO) , Cr(CO) , Fe(CO) , lone pair
5 5 4
phinines clearly favor the coordination of very electron
rich or electron excessive metal centers like CO. Defini-
tive evidences were given by the synthesis of a series of
negatively charged biphosphinine complexes of different
metals: dianionic homoleptic complexes of group 4 met-
als 7 were synthesized [10], monoanionic complexes of
group 7 (M = Mn, Re) 8 [11], dianionic complexes of
group 8 (M = Fe, Ru) 9 [12], monoanionic complexes
of group 9 metals (M = Co, Rh) 10 [13], and a 19 elec-
tron nickel(ꢀ1) complex 11 was characterized by EPR
spectroscopy (Scheme 4) [14]. These complexes were ob-
tained using one of the two following methods: a first
conventional method proceeds via reduction of pre-
formed complexes with the appropriate number of elec-
trons; a second approach relies on the prior synthesis of
a mono radical anion of the biphosphinine or its dianion
followed by complexation [15]. This last method, which
had already proven to be very efficient in the coordina-
tion chemistry of sulfur and nitrogen ligands, could be
extended to phosphorus and provided an access to a
wide range of reduced complexes.
2
: M = W(CO) , Cr(CO) ,
5
5
Scheme 1.
their coordination states, both elements exhibit a
remarkable combination of r and p electronegativity.
In fact, even if phosphorus is less electronegative than
carbon, its p-electronegativity was shown to be more
important than that of carbon especially when both ele-
ments are involved in a doubly or triply bonded system.
This specific electronic situation implies that ligands
incorporating P@C systems present a close analogy with
strong p-acceptor ligands such as carbonyl. Indeed, a
simple molecular orbital diagram clearly shows that
the LUMO of P@C ligands is closer to that of CO than
to that of classical N@C based ligands. The main orbital
coefficient is localized on the element which is directly
bound to the metal. Obviously, P@C systems exhibit a
weaker p-accepting capacity since they essentially be-
have as monodimesional p-acceptor ligands (CO being
considered as a bi-dimensional acceptor ligand because
of its two available orthogonal p -orbitals) (Scheme 2).
*
The existence of such reduced species obviously raises
the question of the formal oxidation state of the metal.
An interesting example was provided by the synthesis
1
0
2
. Results and discussion
of formally d monoanionic (Co(ꢀ1), Rh(ꢀ1)) and
dianionic (Ru(ꢀ2)) complexes with two biphosphinine
ligands. Group 9 complexes adopt a distorted tetrahe-
dral geometry in the solid state and group 8 complex
adopts a square planar geometry. Recent theoretical
studies [16] have shown that this particular situation is
mainly due to the strong p-accepting properties of the
biphosphinine ligands. It results in a small energy differ-
ence between the tetrahedral conformation (expected for
2
.1. Reduced phosphinine transition metal complexes
The analogy between P@C systems and the carbonyl
ligand has been partially explored and exploited so far.
Pioneering works were achieved by the group of C. Els-
chenbroich and our group over the last decade. The
discovery of the first homoleptic phosphinine complexes
1
0
3
–5 (Ni,[5] Fe,[6] Cr[7]) can really be considered as the
a d -ML complex) and the square planar conforma-
4
8
tion (expected for a d -ML complex). In the absence
starting point of this new facet of the ‘‘phosphorus-car-
bon analogy’’ (Scheme 3).
Reasoning that the strong p-accepting capacity of lig-
and such as phosphinines could be employed to stabilize
transition metal complexes in unusual negative oxida-
tion states, we early launched a program aimed at devel-
4
of electrostatic interactions with the counter cation, a
distorted tetrahedral geometry was actually found for
the group 9 complexes. These calculations also revealed
that the weak geometrical preference found for the tetra-
hedral conformation over the square planar one in the
ꢀ
1
dianionic Ru(ꢀ2) complex (3 kcalmol ) is reversed
when interactions with cations occurred. In agreement
with the experimental observation, calculations on the
sodium complex actually show that the square planar
complex 12 is more stable than its tetrahedral isomer
C
O
P
C
N
C
13, the computed energy difference being equal to 19.5
kcal mol (Scheme 5).
ꢀ1
Scheme 2.

M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
2409
P
P
P
P
P
P
P
P
P
P
Ni
Cr
P
P
Fe
P
P
P
5
3
4
Scheme 3.
2
P
CO
CO
CO
P
P
P
M
P
M
P
P
P
P
6
P
8
: M = Mn, Re
7
: M = Ti, Zr, Hf
Li
P
P
P
P
P
P
M
Li
M
P
P
1
1
0: M = Co, Rh
1: M = Ni
9
: M = Fe, Ru
Scheme 4.
Na
Na
P
P
P
P
P
Ru
Ru
Na
P
P
P
1
9.5 kcal.mol-1
Na
12
13
Scheme 5.
Studies were not limited to biphosphinines and
macrocyclic derivatives have also found interesting
applications in the stabilization of electron rich metal
centers. Thus, it has been shown that a silacalix-[5]-
macrocycle could encapsulate a gold(I) center to afford
complex 14. Most interestingly, reduction of this com-
plex provided a monomeric gold(0) 15 complex which
proved to be stable up to 243 K (see Scheme 6). The fact
that Au–CO decomposes at 70 K clearly suggests that
phosphinine-based macrocycles can be considered as
phosphorus equivalent of CO matrices [17]. Similarly,
it has been showed that Rh(I) macrocyclic derivatives
could be reversibly reduced to afford the corresponding
Rh(0) and Rh(ꢀ1) complexes [18].
2.2. Phosphinines in homogeneous catalysis
Homogeneous catalysis is another important field
where phosphorus analogs of the carbonyl ligand
may find interesting applications. Though low coordi-
nated phosphorus ligands such as kinetically stabilized
1,4-phosphabutadienes [19] and phosphaferrocenes al-
ready proved to be valuable systems [20], only a little
is known about the use of phosphinines. The most

2410
M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
Si
Si
Si
Si
P
+e
P
P
Au
P
P
Au
P
-
e
Si
P
Si
Si
P
Si
1
4
15
Scheme 6.
significant report was made by the group of Breit in
collaboration with BASF in the hydroformylation of
olefins process. Functional derivatives of the 2,4,6 tri-
phenylphosphinines such as 16 exhibited an interesting
activity in the hydroformylation of styrene and cyclo-
hexene [21]. Most importantly, in more drastic condi-
tions, they also exhibit a significant activity in the
hydroformylation of tetramethylethylene to afford
agreement with this result, DFT calculations showed
the negative charge to be mostly localized on the
a-carbon atoms of these anions. An analysis of the
charge distribution revealed that the electronic structure
of these anions is closer to that of classical pentadienyl
anions than to that of their analogs, the cyclohexadienyl
anions. Interestingly a natural bond orbital analysis
(NBO) and the analysis of Wyberg bond indices re-
vealed that no delocalization takes place between the
carbocyclic part of the ring and the phosphorus atom.
In such systems, the hydridization of the phosphorus
atom lone pair is close to that of classical tertiary phos-
phines (Scheme 9) [24].
2
(
,3-dimethylbutanal through an isomerization process
Scheme 7).
Unfortunately, if we exclude their use as p-ligands in
the iron catalyzed cyclotrimerization of alkynes and nit-
riles to give pyridines [22], phosphinines, once bound to
a metal center, proved to be too sensitive toward nucle-
ophilic attacks (like CO based analogous complexes) to
be considered as potential ligands in metal-catalyzed
processes involving nucleophilic reagents or bases. A
representative example is provided by the hydrolysis of
a [Pt(biphosphinine)ClMe] complex 17 which occurs
when a dichloromethane solution of the complex is ex-
posed to the presence of traces of water to afford com-
pound 18 (Scheme 8). Interestingly the addition occurs
onto the ring which is trans to the less electron donating
ligand [23].
Reactions of these anions with transition metal pre-
cursors clearly depend on both the nature of the metal
fragment and the substitution Scheme of the ring.
Whereas [ML X] metal fragments react with anions to
n
yield p-complexes such as the rhodium derivative 21
[25], reaction with [ML X ] metal fragments (group 10
n
2
2
metals) yield g -complexes such as 22 in which coordi-
nation occurs through the P–C bond (Scheme 10) [26].
The solid state structure of 22 is not wholly retained in
solution. Dynamic behavior of the [M(PPh )Cl]
3
(M = Pd, Pt) fragment is apparent from the systematic
1
changes observed in the variable temperature
H
2.3. Phosphacyclohexadienyl anions and their related
ligands
NMR data. DFT calculations on model complexes were
performed to determine the structure of the transition
state 23 in the case of the palladium complex. As can
Exploiting the high electrophilicity of the phosphorus
be seen in Scheme 10, this transition state involves a
1
atom allowed us to circumvent this limitation. Thus
phosphacyclohexadienyl anions 19 which are readily ob-
tained through the reaction of nucleophiles with phos-
phinines exhibit a surprising reactivity towards metal
fragments allowing the synthesis of unusual complexes.
Four lithium complexes of these anions, such as com-
plex 20, were characterized by X-ray crystallography
g -coordination of the [Pd(PPh )Cl] fragment onto the
3
phosphorus atom, the interconversion between the two
enantiomeric complexes resulting from a simple rotation
of the fragment (or the ligand) around the Pd-P bond
axis in 23. A good agreement was found between theo-
ꢀ
1
ꢀ1
retical (30.2 kJmol ) experimental (43.7 kJmol
#
)
DG values [26].
Interestingly, the presence of ancillary peripheral lig-
[
24]. When no cryptand is used, coordination of the lith-
ium occurs through the p-system of the ring. In good
ands at the a-carbon atoms of the ring was found to be
H
Ph
[
Rh(CO) (acac)], L = 20 equiv
O
2
L =
P
toluene, 60 bars, 80˚C
1
6
Scheme 7.

M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
2411
OH
H O traces
2
P
P
P
P
H
H
Pt
CH2Cl2, RT
Pt
Cl
Me
Cl
Me
17
18
Scheme 8.
Me
Me
Me
R2
R4
R3
R2
R1
R4
TMS
P
Ph
Ph
_
R-Li
R1
R3
Li
P
P
TMS
Li
R
20
O
1
9
Et
Et
- 0.49
_
-
0.49
_
-
0.43
_
-
-
0.21
0.67
-0.22
-0.37
-0.24
-0.69
P
0
.46
-0.42
H
H
H
Scheme 9.
Me
Me
Me
TMS
P
Ph
Ph
TMS
Rh
2
1
Ph
Ph
Ph
TMS
Ph
TMS
TMS
Ph
TMS
TMS
Ph
TMS
P
P
P
Pd
Pd
Cl
Pd
Cl
Ph P
PPh3
3
Ph P
Cl
3
2
2
23
Scheme 10.
1
determinant in the synthesis of g -P coordinated com-
plexes. Thus, reaction of phosphinine 24 with n-BuLi af-
forded anion 25 which in turn was trapped with
tant coefficient on the C and C carbon atom and the
a c
HOMO ꢀ 1 mainly describes the lone pair at phospho-
rus. Introduction of two ancillary groups possessing
lone pairs result in a combination of these two orbitals
with the in-phase combination of the two lone pairs.
This results in a repulsive interaction that strongly
destabilizes the HOMO ꢀ 1 (more important overlap).
Therefore, in such tridentate SPS anionic ligands, the
HOMO features an important contribution of the lone
pair at phosphorus as well as a significant participation
of the two lone pairs at the ligand this favoring r-
coordination at phosphorus (Scheme 12).
[
M(COD)Cl ] (M = Pd, Pt) to afford the corresponding
2
complexes 26, 27 in which the anion behaves as a triden-
tate ligand. These group 10 complexes were found to be
remarkably resistant toward moisture and air oxidation
Scheme 11) [27–29].
The preference for g -coordination can be easily
rationalized by considering a simple perturbation dia-
gram of these phosphacyclohexadienyl anions MOs. In
such systems, the HOMO is a p-orbital featuring impor-
(
1

2412
M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
Bu
Further studies showed that other synthetic strategies
could be employed to synthesize group 10 square planar
Ph
Ph
Ph
Ph
Ph
Ph
Li
n-BuLi
_
P
Ph
Ph
Ph
P
Ph
Ph
Ph
P
complexes. Thus, reaction of phosphinine 24 with
[Pd(COD)Cl ] affords the chloro-P chloropalladium
P
S
S
P
P
2
2
4
S
25
S
complex 28 which can in turn be functionalized at phos-
phorus through nucleophilic substitution [27]. Another
interesting method involves the oxidative addition of a
[
M(COD)Cl2]
Bu
Ph
Ph
Ph
M
5
P–Cl bond of a k -P-dichloro-phosphinine 29 onto a
P
Ph
Ph
Ph
P
2
6: M = Pd
27: M = Pt
Pd(0) fragment to give complex 30 [28]. Most surpris-
ingly, even P-oxide derivatives of 1,2-dihydrophosphi-
nines such as 31 proved to be valuable precursors of
tridentate SPS-based complexes such as 32 featuring a
central P–OH group as ligand (Scheme 13).
S
P
S
Cl
Scheme 11.
_
_
P
P
R
A
R
A
A
A
HOMO
P
R
A
A
HOMO
P
R
R
HOMO-1
P
A
A
Scheme 12.
Cl
Nu
P
Ph
Ph
P
Ph
Ph
Ph
Pd
Nu-
[
Pd(COD)Cl2]
Ph
Ph
P
Ph
P
2
4
S
S
Ph
P
Ph
Ph
Pd
P
S
Ph
S
Cl
Cl
2
8
Cl
Ph
Ph
Ph
Ph
Ph
Ph
Pd
[
Pd(dba)2]
P
Cl
Ph
Ph
P
Ph
P
P
S
S
Ph
P
P
Cl
S
Ph
S
Ph
Cl
2
9
30
OH
P
Ph
Ph
Ph
Ph
Ph
Ph
Pd
[
Pd(COD)Cl2]
P
Ph
P
Ph
Ph
Ph
P
H
S
H
S
Ph
Ph
P
P
O
S
S
Cl
3
1
32
Scheme 13.

M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
2413
5
All these r-complexes can be regarded either as a k -
metallated phosphinine (form I) or as a classical r-com-
plex of a phosphacyclohexadienyl anion (form II).
Though both forms very likely contribute in the bond-
ing, preliminary calculations suggest that form II is
probably predominant (Scheme 14). DFT calculations
and charge decomposition analysis (CDA) suggest that
a delocalization takes place within the carbocyclic part
of the ligand and that the central phosphorus atom be-
haves as a classical tertiary phosphorus atom [28].
Other r complexes were prepared according to the
same synthetic strategy. The most significant results
were obtained in studying the chemistry of group 9 met-
als. Thus, reaction of anion 33 with the [Rh(COD)Cl]2
dimer yielded the very stable 18 electron complex 34
whose structure remains unknown. However, displace-
ment of the COD ligand from 34 afforded the highly
reactive square planar 16 electron complex 35 which
was structurally characterized. Complex 35 proved to
be highly reactive toward small molecules such as O2,
CO , CS and SO . Whereas reaction with O , CO
geometry. Interestingly, in all cases, attack of the incom-
ing ligand has taken place on the syn face of the complex
(Scheme 15) [30]. Calculations are currently underway in
our laboratories to determine the origin of this facial
discrimination.
2.4. Mixed SP and SPS ligands and their complexes in
catalysis
The flexibility of the SPS ligand was also evidenced in
a recent study dealing with the coordination chemistry
of Cu(I) and Au(I) derivatives. An insoluble oligomeric
copper complex 38 was obtained by reacting the anionic
ligand 34 with CuI in THF at room temperature. Reac-
tion of 38 with two electron-donor ligands such as 2,6-
dimethylphenylisocyanide, t-butylisocyanide, PPh3,
P(OPh) and pyridine afforded the expected tetrahedral
3
Cu(I) complexes 39 in which the ligand caps three bind-
ing sites (Scheme 16) [31].
The catalytic activity of palladium (II) complexes of
these SPS ligands was tested in different processes. In
the Heck-coupling between methyl-acrylate and iodo-
benzene, methyl trans-cinnamate was produced in
a quantitative yield with a TON of 10000. A quite
2
2
2
2
2
and CS yielded trigonal bipyramidal Rh(III) complexes
2
in which the SPS ligand caps one face of the bipyramid
2
such as in the g -O complex 36, reaction with SO af-
2
2
forded a Rh(I) complex 37 which adopts a pyramidal
Ph
Ph P
Ph
PPh2
Ph
Ph
PPh2
P
_
P
Cu
CuI
L
S
S
S
S
P
Ph P
P
33
Cu
2
2
THF
S Me
S
S Me
S
L
n
form I
form II
38
39
Scheme 14.
Scheme 16.
Me
P
Me
Ph
Ph
Ph
Ph
Li
[Rh(COD)Cl]2
Ph
S
P
Ph
Ph
Ph
Ph
P
Ph
P
S
Ph
P
P
Rh
COD
S
S
Ph
3
3
PPh3
Me
3
4
-
COD
Ph
Ph
Ph
Rh
P
Ph
Ph
Ph
P
S
P
S
Ph P
3
35
Me
Me
O
Me
P
O
P
P
S S
Rh
S
S
SO2
O2
O
O
Rh
Rh
S
S
PPh3
S
PPh3
PPh3
37
35
Scheme 15.
36

2414
M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
R
R
O
O
[26] cat
O
O
X + H B
B
dioxane, Et N,
3
X = Br, I
TON up to 76 500
Scheme 17.
Me
Ph
Bu
Ph
Ph
Ph
Cl
Ph
Ph
Ph
Ph
Ph
P
P
Ph
Ph
Ph
Ph
P
Ph
Ph
Ru
P
Pd
P
P
S
S
S
4
0
41
42
R
R
HO
[
42] cat
Br
+
B
HO
K CO , toluene
2
3
∆
, 24h
TON up to 799 103
Scheme 18.
promising result was obtained in the Miyaura cross-cou-
pling reaction which allows the formation of boronic es-
ters from halogenoarenes and pinacolborane [27].
Whereas no reaction was observed with arylchlorides,
catalyst 26 proved to be sufficiently reactive to convert
iodo and bromo derivatives in dioxane at reflux in good
yields. With aryliodides TON up to 76500 were re-
corded (Scheme 17).
Acknowledgement
The authors thank the CNR and the Ecole Polytech-
nique for the financial support of this work.
References
Importantly, we recently found that bidentate PS
ligands could also be produced in a similar way by
reacting alkyllithium derivatives with phosphinine 40
[
1] See for example: F. Mathey, Angew. Chem. Int. 42 (2003)
1
578.
[2] (a) P. Le Floch, A. Marinetti, L. Ricard, F. Mathey, J. Am.
Chem. Soc. 112 (1990) 2407;
[
32]. Here again, coordination occurs through the
(
(
(
b) P. Le Floch, F. Mathey, Synlett. (1990) 171;
c) A. Marinetti, F. Mathey, Angew. Chem. 100 (1988) 1435;
d) A. Marinetti, S. Bauer, L. Ricard, F. Mathey, Organometallics
phosphorus atom lone pair the sulfur ligand serving
as a second binding site. Ru(II) cymene 41 and the
Pd(II) allyl 42 complexes were easily produced and
characterized by X-ray crystallography. Though the
ruthenium complex exhibited a moderate activity in
the transfer hydrogenation of ketones using isopropa-
nol as a proton source, complex 42 showed an inter-
esting activity in the Suzuki coupling process that
furnishes functional biphenyl derivatives through the
reaction of phenylboronic acid with bromoarenes
9 (1990) 793;
(e) A. Marinetti, P. Le Floch, F. Mathey, Organometallics 10
(
(
1991) 1190;
f) S. Shah, J.D. Prostaziewicz, Coord. Chem. Rev. 210 (2000)
1
81;
(
(
g) S. Shah, J.D. Prostaziewicz, Chem. Commun. (1998) 1585;
h) S. Shah, T. Concolino, A.L. Rheingold, J.D. Prostaziewicz,
Inorg. Chem. 39 (2000) 3860.
3] (a) F. Mathey, J. Organomet. Chem. 93 (1975) 377;
[
(
(
(
(
b) F. Mathey, Tetrahedron Lett. 17 (1976) 4155;
c) F. Mathey, A. Mitschler, R. Weiss, J. Am. Chem. Soc. 100
1978) 5748;
(
substrate) (Scheme 18).
TON up to 799000 with 4-bromoacetophenone as
In conclusion, it appears that, despite their high sen-
sitivity which usually precludes their use as ligands in
catalysis, phosphinines proved to be a valuable source
of new heterocyclic ligands and complexes. Further
studies will now focus on the systematic study of the
binding properties of these new bidentate SP and triden-
tate SPS ligands in coordination chemistry and catalysis.
d) G. de Lonzon, F. Mathey, M. Simalty, J. Organomet. Chem.
156 (1978) C33;
e) G. de Lonzon, B. Deschamps, J. Fischer, F. Mathey, J. Am.
Chem. Soc. 102 (1980) 994.
(
[
[
4] K.B. Dillon, F. Mathey, J.F. Nixon, Phosphorus: The carbon
Copy, Wiley, Chichester, 1988.
5] C. Elschenbroich, M. Nowotny, A. Behrendt, W. Massa, S.
Wocaldo, Angew. Chem. Int. Ed. Engl. 31 (1992) 1343.

M. Doux et al. / Journal of Organometallic Chemistry 690 (2005) 2407–2415
2415
[
[
[
[
6] C. Elschenbroich, M. Nowotny, J. Kroker, A. Behrendt, W.
Massa, S. Wocaldo, J. Organomet. Chem. 459 (1993) 157.
7] C. Elschenbroich, S. Voss, O. Schiemann, A. Lippek, K. Harms,
Organometallics 17 (1993) 4417.
(b) F. Ozawa, H. Okamoto, S. Kawagishi, S. Yamamoto, T.
Minami, M. Yoshifuji, J. Am. Chem. Soc. 124 (2002) 10968;
(c) M. Yoshifuji, J. Syn. Org. Chem. Jpn. 61 (2003) 1116.
[20] (a) X. Sava, L. Ricard, F. Mathey, P. Le Floch, Organometallics
19 (2000) 4899;
8] N. M e´ zailles, F. Mathey, P. Le Floch, Prog. Inorg. Chem. 49
(2001) 455.
(b) R. Shintani, M.M.C. Lo, G.C. Fu, Org. Lett. 2 (2000) 3695;
(c) M. Ogasawara, K. Yoshida, T. Hayashi, Organometallics 20
(2001) 3913;
9] (a) P. Le Floch, D. Carmichael, L. Ricard, F. Mathey, J. Am.
Chem. Soc. 113 (1991) 667;
(
b) P. Rosa, N. M e´ zailles, L. Ricard, F. Mathey, P. Le Floch, J.
Org. Chem. 63 (1998) 4826.
(d) K. Tanaka, G.C. Fu, J. Org. Chem. 66 (2001) 8177;
(e) R. Shintani, G.C. Fu, Org. Lett. 4 (2002) 3699;
(f) D. Carmichael, J. Klankermayer, L. Ricard, N. Seeboth,
Chem. Commun. 9 (2004) 1144.
[
[
[
[
[
10] P. Rosa, N. M e´ zailles, L. Ricard, F. Mathey, P. Le Floch,
Angew. Chem. Int. Ed. 39 (2000) 1823.
11] F. Hartl, T. Mahabiersing, P. Rosa, L. Ricard, P. Le Floch,
Inorg. Chem. 42 (2003) 4442.
[21] (a) B. Breit, R. Winde, T. Mackewitz, R. Paciello, K. Harms,
Chem. Eur. J. 7 (2001) 3106;
12] P. Rosa, N. M e´ zailles, L. Ricard, F. Mathey, P. Le Floch, Y.
Jean, Angew. Chem. Int. Ed. Engl. 40 (2001) 1251.
13] N. M e´ zailles, P. Rosa, L. Ricard, F. Mathey, P. Le Floch,
Organometallics 19 (2000) 2941.
(b) B. Breit, R. Winde, K. Harms, J. Chem. Soc. Perkin Trans. 1
(1997) 2681.
[22] F. Knoch, F. Kremer, U. Schmidt, U. Zenneck, P. Le Floch, F.
Mathey, Organometallics 15 (1996) 2713.
14] S. Choua, H. Sidorenkova, T. Berclaz, M. Geoffroy, P. Rosa, N.
M e´ zailles, L. Ricard, F. Mathey, P. Le Floch, J. Am. Chem. Soc.
[23] D. Carmichael, P. Le Floch, F. Mathey, unpublished results.
[24] A. Moores, L. Ricard, P. Le Floch, N. M e´ zailles, Organometallics
22 (2003) 1960.
1
22 (2000) 12227.
15] (a) P. Rosa, L. Ricard, F. Mathey, P. Le Floch, Organometallics
8 (1999) 348;
b) P. Rosa, N. M e´ zailles, L. Ricard, F. Mathey, P. Le Floch,
[
[25] A. Moores, N. M e´ zailles, L. Ricard, P. Le Floch, submitted.
[26] A. Moores, N. M e´ zailles, L. Ricard, Y. Jean, P. Le Floch,
Organometallics 23 (2004) 2870.
1
(
Angew. Chem. Int. Ed. Engl. 40 (2001) 4476.
16] H. Perron, A. Moores, I. Demachy, A. Lledos, Y. Jean, P. Le
Floch, New. J. Chem. (2004) 838.
[27] M. Doux, N. M e´ zailles, M. Melaimi, L. Ricard, P. Le Floch,
Chem. Commun. (2002) 1566.
[
[
[28] M. Doux, N. M e´ zailles, L. Ricard, P. Le Floch, Eur. J. Inorg.
Chem. (2003) 3878.
17] N. M e´ zailles, N. Avarvari, N. Maigrot, L. Ricard, F. Mathey, P.
Le Floch, L. Cataldo, T. Berclaz, M. Geoffroy, Angew. Chem.
Int. Ed. 38 (1999) 3194.
[29] M. Doux, C. Bouet, N. M e´ zailles, L. Ricard, P. Le Floch,
Organometallics 21 (2002) 2785.
[
18] (a) N. Avarvari, N. M e´ zailles, L. Ricard, P. Le Floch, F. Mathey,
Science 8 (1998) 1587;
[30] M. Doux, N. M e´ zailles, L. Ricard, P. Le Floch, Organometallics
22 (2003) 4624.
(b) L. Cataldo, S. Choua, T. Berclaz, M. Geoffroy, J. Phys.
Chem. A 106 (2002) 3017.
[31] M. Doux, L. Ricard, P. Le Floch, N. M e´ zailles, Dalton Trans
(2003) 2593.
[
19] (a) T. Minami, H. Okamoto, S. Ikeda, R. Tanaka, F. Ozawa, M.
Yoshifuji, Angew. Chem. Int. Edit. 40 (2001) 4501;
[32] M. Dochnahl, M. Doux, E. Faillard, L. Ricard, P. Le Floch, in
press.