Coordination chemistry of large diphosphanes - Directional properties of a calix[4]arene proximally substituted by two -OCH2PPh2 podand arms

Article abstract of DOI:10.1002/ejic.200400411

The proximally-functionalised calixarene 5,11,17,23-tetra-tert-butyl-25,26- bis(diphenylphosphanylmethoxy)-27,28-dihydroxycalix[4]arene (1), a large diphosphane in which the P^III centres are separated by 10 bonds, behaves as a chelating ligand

Full text of DOI:10.1002/ejic.200400411

FULL PAPER
Coordination Chemistry of Large Diphosphanes ؊ Directional Properties of a
Calix[4]arene Proximally Substituted by Two ؊OCH2PPh2 Podand Arms
[a]
[a]
[a]
[a]
[b]
´
Pierre Kuhn, Catherine Jeunesse, David Semeril, Dominique Matt,* Pierre Lutz,
and Richard Welter[c]
Dedicated to Professor Jean-Pierre Sauvage on the occasion of his 60th birthday
Keywords: Calixarenes / Large diphosphanes / Nickel complexes / Ethylene oligomerisation
The proximally-functionalised calixarene 5,11,17,23-tetra-
tert-butyl-25,26-bis(diphenylphosphanylmethoxy)-27,28-
dihydroxycalix[4]arene (1), a large diphosphane in which the
not a square planar one. In all structures, the ligand positions
the nickel atom away from the calixarene axis. In the pres-
ence of methylaluminoxane (MAO), [NiCl2·1] effectively
PIII centres are separated by 10 bonds, behaves as a chelating catalyses the oligomerisation of ethylene, affording C4−C12
ligand towards NiX2 moieties (X = Cl, Br). As shown by three
X-ray studies carried out on complexes of the type [NiX2·1],
the diphosphane is able to accommodate either tetrahedral
or strongly distorted tetrahedral coordination geometries, but
oligomers.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
investigated its coordination behaviour towards NiCl2 and
NiBr2 units, two versatile fragments known to form either
Calix[4]arenes locked in the cone conformation are re- tetrahedral or square planar [NiX2(phosphane)2] metal
markable building blocks for the preparation of multifunc- complexes. The present study describes the syntheses and
tional ligands.[1Ϫ5] They are frequently used as preorganis- structures of three paramagnetic nickel() complexes based
ing platforms allowing control of the orientation of pod- on 1 and illustrates that the ligand bite angle may undergo
ands anchored to one of the rims and hence for imposing a major variation, hence enabling the metal centre to ap-
particular coordination geometry upon a complexed metal proach closer to the calixarene core.
ion.[6,7] Depending upon their nature, length and flexibility,
convergent binding sites tethered at the same rim may not
only result in high complexation selectivities but also pro-
duce metal complexes with unconventional catalytic
properties.[8Ϫ18] In a recent paper, we reported the coordi-
nation chemistry of the diphosphane 1 and have shown that
this conical calixarene,[19] as well as some derivatives,[20,21]
forms square planar PtII chelate complexes (A) exclusively
in the cis configuration in which the P-M vectors are ori-
ented away from the calixarene axis, thus positioning the
metal outside the conical domain defined by the macrocy-
cle. The ligand bite angle in cis-[PtCl2·1], as revealed by an
X-ray study, is 103.4(1)°. In order to further substantiate
the directional properties of this diphosphane, we have now
Results and Discussion
[a]
´
Universite Louis Pasteur, Laboratoire de Chimie Inorganique
´
Moleculaire,
From our previous study it appears that despite its con-
siderable length, diphosphane 1 is sufficiently preorganised
to readily form chelate complexes with the PtCl2 moiety.[19]
Complexation of this fragment results in formation of a
compound in which the platinum atom is oriented outwards
from the cone defined by the calixarene. The same com-
UMR 7513 CNRS,
1 rue Blaise Pascal, 67008 Strasbourg Cedex, France
E-mail: dmatt@chimie.u-strasbg.fr
Institut Charles Sadron, UPR 22 CNRS,
6 rue Boussingault, 67083 Strasbourg Cedex, France
DECMET, UMR 7513,
[b]
[c]
4 rue Blaise Pascal, 67070 Strasbourg Cedex, France
4602
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400411
Eur. J. Inorg. Chem. 2004, 4602Ϫ4607

Coordination Chemistry of Large Diphosphanes
FULL PAPER
plexation behaviour towards PtCl2 was observed when gets the impression that the ligand is attempting unsuccess-
using analogues of 1 in which the phenol rings bear sub- fully to behave as a trans spanning ligand. Clearly, com-
stituents.[19,21] Inverting the orientation of the P lone pairs plexation results in a strained chelate ring, as shown by the
is a challenging goal that would lead to complexes where C(1)P(1)Ni and C(46)P(2)Ni angles of 109.9(1)° and
the metal is brought closer to the calixarene axis, thus fav- 108.1(1)°, respectively, which are about 10° smaller than the
ouring interactions between the coordination centre and the other CPNi angles. It should be remembered here that, as
bulky calixarene core. In order to study whether 1 gives shown in previous studies, calix[4]arenes having at least two
access to such structures, we decided to investigate the coor- proximal ϪOCH2PPh2 units display a marked propensity
dination properties of 1 towards the nickel() centre which to form cis-chelated structures, no trans complexes having
has a greater stereoflexibility than platinum().
been reported to date. The NiP bond lengths [2.220(1),
˚
2.247(1) A] lie in the range found for complexes of the gen-
The preparation of complex 2 required a two-step pro-
cedure consisting of (i) dissolution of anhydrous NiCl2 in
small amounts of EtOH to form an unidentified species
which, unlike NiCl2, is soluble in CH2Cl2 and (ii) treatment
of the thus formed species with a solution of 1 in CH2Cl2
(Equation 1). A direct synthesis in CH2Cl2 was impossible
due to the insolubility of NiCl2 in this solvent, while at-
tempted synthesis in pure EtOH did not result in phos-
phane coordination. We found that the best EtOH/CH2Cl2
ratio was ca. 1:10.
eral formula trans-[NiCl2(PPh2R)2].[23Ϫ25]
Figure 1. Molecular structure of the blue complex
[NiCl2·1]·2CH2Cl2 (2·2CH2Cl2); only the Cipso atoms of the P-phe-
nyl rings are shown; the tBu groups are not shown in full
The dark blue complex 2 is paramagnetic and was
characterised by elemental analysis and an X-ray diffraction
study. Its molecular structure is shown in Figure 1. The
shape of the calixarene core deviates only slightly from an
ideal cone. Thus, the "centroid-centroid" separations be-
Complexes 3 and 4 were obtained as a binary mixture,
but could be separated mechanically after crystallisation.
They were prepared similarly to the method outlined above
for 2, but starting from anhydrous NiBr2 (Equation 2).
Crystallisation from dichloromethane/heptane afforded a
mixture of crystals of turquoise 3 and red-brown 4.
˚
tween the distal phenol units are 6.45 and 6.93 A, respec-
tively, while the dihedral angles between the calixarene ref-
erence plane [defined as the mean plane of the bridging C
atoms, here C(12), C(23), C(34), C(45)] and those of the
four phenol rings are 115° (C2), 103° (C18), 134° (C29) and
124° (C40). Hydrogen bonds involving the hydroxy groups
and the neighbouring phenolic oxygen atoms may contrib-
ute to this structure, as indicated by the rather short
˚
˚
O(1)···O(3) [2.78(2) A], O(2)···O(4) [2.87(2) A] and
˚
O(3)···O(4) [2.67(2) A] separations (cf. O(1)···O(2) 3.46(2)
A]. The compound crystallises with two dichloromethane
˚
molecules, one of them lying inside the calixarene basket.
The shortest contacts of the latter with the aromatic walls
˚
are between H(71b) and C(27) (2.83 A), and H(71b) and
˚
C(28) (2.84 A). Note, considerably shorter contacts have
been found in other calixarenes with CH2Cl2 guests.[22] The
Ni atom is slightly bent towards the exterior of the cavity
and its coordination geometry may be regarded as being
between square planar and tetrahedral. By considering the
PNiP and ClNiCl angles of 158.45(3)° and 158.29(4)°, one
Eur. J. Inorg. Chem. 2004, 4602Ϫ4607
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´
P. Kuhn, C. Jeunesse, D. Semeril, D. Matt, P. Lutz, R. Welter
FULL PAPER
Obtaining this crystal mixture is easily reproducible. It
appears likely that both compounds exist in equilibrium in
solution, since dissolving crystals of either of them afforded
the same green solution (toluene or CH2Cl2). The two mo-
lecular structures were determined by single-crystal X-ray
diffraction studies (Figure 2 and 3). Again, both calixarenes
adopt the shape of a cone having a ‘‘circular’’ cross section
and both cavities host a dichloromethane molecule. As
found in 2, hydrogen bonds involving the hydroxy groups
appear to stabilise the whole calixarene geometry (Table 1).
The coordination geometry of 3 is close to that found in 2,
as can be seen from the PNiP and BrNiBr angles of
158.58(3)° and 152.19(2)°, respectively. In contrast, 4 has a
conventional tetrahedral stereochemistry with considerably
smaller PNiP [118.6(3)°] and BrNiBr [138.55(5)°] angles. In-
cidentally, the metallomacrocyclic unit of 4 is less strained
than those of 2 and 3. For example, the values of the NiPCα
angles in this unit are 119.0(1)° and 117.6(1)°. We note that
in all three complexes, the Ni atom is orientated away from
the calixarene axis. In each structure, a halogen atom ap-
proaches the axial H(12) atom but weak interactions with
this methylene
H
are likely to occur in
2
and
3
Figure 3. Molecular structure of the red brown complex
[NiBr2·1]·1.75CH2Cl2 (4·1.75CH2Cl2); for clarity, only the Cipso
atoms of the P-phenyl rings are shown; the tBu groups are not
shown in full
˚
[Haxial(12)···X distances (A): 2.77, 2.84 and 3.00, respec-
tively, for 2, 3 and 4]. These weak interactions could explain
why the NiϪX(2) bonds of 2 and 3 are slightly but signifi-
cantly longer than the corresponding NiϪX(1) bonds. In-
volvement of ArCHaxial hydrogen atoms in weak bonding
have recently been found in other calixarenes, in particular
in some agostic CH···M interactions.[21] Finally, it is note-
worthy that there is no indication in the syntheses outlined
above of oligomer formation, illustrating the high degree of
preorganisation of calixarene 1.
Table 1. Relevant structural parameters for 2, 3 and 4 in the solid
state
2
3
4
˚
Distances (A)
O1···O2
3.46(2)
2.78(2)
3.96(2)
4.33(2)
2.87(2)
2.67(2)
2.247(1)
2.220(1)
2.150(2)
2.168(2)
3.47(2)
2.78(2)
3.98(2)
4.33(2)
2.89(2)
2.68(2)
2.235(1)
2.215(1)
2.286(1)
2.308(1)
3.30(2)
2.74(2)
4.11(2)
4.14(2)
3.05(2)
2.63(2)
2.290(9)
2.303(9)
2.320(6)
2.338(6)
O1···O3
O1···O4
O2···O3
O2···O4
O3···O4
NiϪP1
NiϪP2
NiϪX1
NiϪX2
Angles (°)
PNiP
158.45(3)
158.29(4)
2
158.58(3)
152.19(2)
3
118.6(3)
138.55(5)
4
XNiX
Dihedral angles (°)
between the phenol
rings and the
calixarene reference plane
(C2)
(C18)
(C29)
115(1)
103(1)
134(1)
124(1)
115(1)
104(1)
136(1)
124(1)
114(1)
110(1)
122(1)
133(1)
(C40)
It is well known that [NiCl2(phosphane)2] complexes con-
stitute good precatalysts for the oligomerisation or polym-
erisation of olefins, the outcome of the reaction being
strongly dependent on the nature of the phosphane.[26,27]
Thus for example, [NiCl2(PCy3)2] activated with AlEt2Cl
becomes
catalyst.[28] A typical activity for this complex is 1600
Ϫ1 [29] Other complexes, for instance
a
highly selective ethylene dimerisation
Figure 2. Molecular structure of the turquoise complex
[NiBr2·1]·2CH2Cl2 (3·2CH2Cl2); for clarity, only the Cipso atoms of
the P-phenyl rings are shown; the tBu groups are not shown in full mol(C2H4)·mol(Ni)Ϫ1·h
.
4604
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Coordination Chemistry of Large Diphosphanes
Table 2. Ethylene oligomerisation with 2 (conditions: complex 2 (6 µmol), MAO (0.500 g), toluene (20 mL), initial temperature 25 °C)
FULL PAPER
P(C2H4)
(bar)
α
(°)
TOF
Activity
g C2H4/(mmol [Ni]·h·bar)
Olefin distribution
(wt.-%)
(mol C2H4)/(mol [Ni]·h)
C4
73.9
68.4
C6
19.9
22.6
C8
4.8
6.6
C10
1.1
1.8
C12
0.3
0.5
C14
/
0.1
10
30
0.18
0.22
3100
9800
8.7
9.1
[NiBr2{Ar2PN(Me)PAr2}] (Ar ϭ o-iPrC6H4), display a high adapt to various tetrahedral coordination geometries, some
ethylene polymerisation activity [with activities as high as of them being extremely distorted. Thus, 1 gives access to
79000 mol(C2H4)·mol(Ni)Ϫ1·hϪ1] producing high molecular bite angles lying in the range 103.4°Ϫ158.6°. The fact that
weight polymers.[30] Recent work on [NiCl2(chelate)] com- to date no complex could be synthesised in which 1 behaves
plexes has clearly underlined that a subtle combination of as a genuine trans chelator obviously arises from the rigidity
backbone rigidity and partial steric protection of the nickel of the spacer that links the PIII atoms as well as the short-
centre is the determining factor for product distribution ness of the two phosphorus arms. The present work further
control.[31,32] It is also worth mentioning that to date, long demonstrates that ligand 1 is able to bring the metal centre
chain diphosphanes having a backbone containing more closer to the calixarene axis than was previously observed
than six carbon atoms have not been studied in olefin oligo- in PtII complexes, although the PM vectors remain oriented
merisation/polymerisation systems.[27,33] Reports dealing outwards. Activation of 2 with MAO afforded a good ethyl-
with generic calix[4]arenes that were employed in olefin pol- ene oligomerisation catalyst resulting selectively in C4ϪC12
ymerisation have appeared in the literature, but these re- oligomers. The formation of short oligomers suggests that
main scarce.[34Ϫ37]
during catalysis the nickel environment is slightly encum-
In view of the fact that ligand 1 possesses a flexible bite bered hence favouring reductive elimination over chain
angle, we decided to assess the role of complex 2 in ethylene propagation. The formation of polymers could possibly be
oligomerisation. The runs were performed in toluene ([cata- forced by orientating the PM vectors towards the calixarene
lyst] ϭ 0.3 mmol/dm3) using methylaluminoxane (MAO) axis so as to ensure partial protection of the metal. Further
(1500 equiv.) as the activator. Operating under an ethylene studies are aimed at exploiting the bite angle flexibility of
pressure of 10 bar and stopping the reaction after 1 h, pro- diphosphane 1 in catalytic reactions.
duced C4 to C12 oligomers. The observed activity was 3100
mol(C2H4)·mol(Ni)Ϫ1·hϪ1. The product distribution is typi-
cally of the SchulzϪFlory type, with α about 0.2 (Table 2).
Applying a pressure of 30 bar increased the activity up
to 9800 mol(C2H4)·mol(Ni)Ϫ1·hϪ1 without modifying the
product distribution. Interestingly, no catalyst deactivation
was observed during these 1 h experiments. As shown by
the study outlined above, diphosphane 1 is able to undergo
Experimental Section
General Conditions: Solvents were dried with suitable reagents and
freshly distilled under dry nitrogen before use. All reactions were
large bite angle variations but this has only little impact on carried out using modified Schlenk techniques under a dry nitrogen
atmosphere. Elemental analyses were performed by the Service
the catalyst activity. For comparison, in terms of activity
and selectivity, the catalyst performance compares with that
of [NiCl2(Ph2PCH2PPh2)], a complex in which the chelating
unit is much more strained than that in 2.[38] The structural
studies revealed that, whatever the coordination geometry
of nickel complexes containing 1, the bulky calixarene core
is remote from the nickel centre, resulting in a rather un-
crowded metal environment and hence facilitating reductive
elimination steps.
´
de Microanalyse, Centre de Recherche Chimie, Universite Louis
Pasteur, Strasbourg. 5,11,17,23-Tetra-tert-butyl-25,26-bis(diphenyl-
phosphanylmethoxy)-27,28-dihydroxycalix[4]arene (1) was pre-
pared according to the previously reported method.[19] MAO 10
wt.-% (Aldrich) was used as a white powder which was obtained
after evaporation of the solvent (60 °C, 3 h). This treatment reduces
the amount of residual trimethylaluminium to ca. 3%.
Synthesis of Dichloro-{5,11,17,23-tetra-tert-butyl-25,26-bis(diphen-
ylphosphanylmethoxy)-27,28-dihydroxycalix[4]arene}nickel(II
)
(2):
Anhydrous NiCl2 (0.019 g, 0.15 mmol) was dissolved in hot ethanol
(0.5 mL) whereupon a solution of 1 (0.153 g, 0.15 mmol) in CH2Cl2
(5 mL) was added. During addition the pale yellow solution turned
deep blue. After 0.25 h, the solvent was removed in vacuo. The
residue was treated with a small volume of pentane (5 mL) and the
resultant suspension filtered through a glass frit. Cooling to Ϫ30
°C precipitated a dark blue powder which was dried in vacuo.
Yield: 0.070 g, 40%. C70H78Cl2NiO4P2 (Mr ϭ 1174.93): calcd. C
71.56, H 6.69; found C 71.66, H 6.90. Single-crystals suitable for
X-ray diffraction were obtained by slow diffusion at room tempera-
Conclusion
In this study we have shown that in the presence of NiX2
moieties the large diphosphane 1 straightforwardly forms
chelate complexes, thus confirming the good preorganis-
ation of the ligand. While previous studies have shown that
1 and its congeners act exclusively as cis-chelators towards
the PtCl2 moiety, we have discovered that 1 is also able to ture of hexane into a CH2Cl2 solution of the complex.
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´
P. Kuhn, C. Jeunesse, D. Semeril, D. Matt, P. Lutz, R. Welter
FULL PAPER
Table 3. Crystal and structure refinement data for 2, 3 and 4
Formula
C70H78Cl2NiO4P2·2CH2Cl2 C70H78Br2NiO4P2·2CH2Cl2 C70H78Br2NiO4P2·1.75CH2Cl2
Molecular mass
Crystal system
Space group
1344.73
triclinic
P1
12.7590(10)
16.7150(10)
18.4130(10)
110.11(5)
104.31(5)
100.36(5)
3418(2)
2
1433.65
triclinic
P1
12.736(5)
16.895(5)
1387.97
monoclinic
P21/n
18.868(2)
14.1060(10)
29.853(3)
90
105.62(5)
90
7651.8(12)
4
1.205
1.470
2882
¯
¯
˚
a (A)
˚
b (A)
˚
c (A)
18.441(5)
α (°)
β (°)
γ (°)
110.599(5)
104.026(5)
100.257(5)
3448.8(19)
2
1.380
1.688
3
˚
V (A )
Z
D(calcd.) (g·cmϪ3
)
)
1.307
0.612
1412
µ(Mo-Kα) (mmϪ1
F(000)
1484
Crystal size (mm)
Temperature (K)
Radiation, λ (Mo-Kα) (A)
Θmin.,max. (°)
Data set (h; k; l)
Total, unique data, R(int.)
Obsd. data with I Ͼ 2.0σ(I)
Nreflections, Nparameters
R1, wR2, S
0.08 ϫ 0.10 ϫ 0.13
173
0.71069
0.05 ϫ 0.07 ϫ 0.08
173
0.71069
0.06 ϫ 0.07 ϫ 0.08
173
0.71069
˚
1.3, 30.0
1.8, 30.0
1.0, 30.0
Ϫ17/17; Ϫ23/22; 0/25
19905, 19905, 0.035
14740
19905, 766
0.0712, 0.1863, 1.05
Ϫ1.07, 1.17
Ϫ17/17; Ϫ23/23; Ϫ25/24
41543, 20069, 0.050
15013
20069, 766
0.0663, 0.1496, 1.03
Ϫ1.13, 1.29
Ϫ21/26; Ϫ19/19; Ϫ34/42
36106, 20421, 0.073
10790
20421, 748
0.0989, 0.3089, 1.02
Ϫ1.25, 1.56
Ϫ3
˚
Min., max. residual electron density (e·A
)
Synthesis of Dibromo-{5,11,17,23-tetra-tert-butyl-25,26-bis(diphen-
Crystal Structure Determination of 3·2CH2Cl2 and 4·1.75CH2Cl2:
ylphosphanylmethoxy)-27,28-dihydroxycalix[4]arene}nickel(II), Iso- Single crystals of 3 and 4 were obtained simultaneously by slow
mers 3 and 4: Anhydrous NiBr2 (0.041 g, 0.19 mmol) was dissolved
in hot ethanol (0.5 mL) resulting in a pale orange solution. A solu-
tion of 1 (0.200 g, 0.19 mmol) in CH2Cl2 (5 mL) was then added
and the mixture turned green. After 0.25 h, the solution was evapo-
rated to dryness. The residue was redissolved in CH2Cl2 (ca. 1 mL),
whereupon pentane was added to precipitate a pale green powder
diffusion of heptane into a solution of [NiBr2·1]. Data collection
and structure solution were carried out as above for 2 (Table 3).
The poorer quality of the structure of 4 is due to disordered solvent
molecules, whether they lie inside or outside the cavity. CCDC-
234358 (for 3) and CCDC-234359 (for 4). These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
which was recovered by filtration. Yield: 0.197 g, 82%. The green [or from the Cambridge Crystallographic Data Centre, 12, Union
powder was then dissolved in CH2Cl2. Slow diffusion of heptane
into the resultant intense green solution afforded crystals of 3 (tur-
quoise colour) and 4 (red brown) which were separated mechan-
ically. Elemental analyses were carried out on both isomers after
drying in high vacuum: C70H78Br2NiO4P2 (Mr ϭ 1263.83): calcd.
C 66.53, H 6.22; found for 3: C 66.22; H 5.75; found for 4: C 66.50;
H 6.42.
Road, Cambridge CB2 1EZ, UK; Fax: ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Oligomerisation of Ethylene: The catalytic runs were carried out in
a 100 mL glass-lined stainless steel autoclave containing a magnetic
stirring bar. In a typical run, a solution of complex 2 (0.007 g, 6
µmol) in toluene (15 mL) was introduced under nitrogen into the
autoclave whereupon a solution of MAO (0.500 g) in toluene (5
mL) was added. After stirring for ca. 1 min the autoclave was press-
urised with ethylene and the pressure (10 or 30 bar) was maintained
at a constant value. During the runs described in this work, the
temperature raised from 25 °C to 37 °C when operating at 10 bar
and up to 42 °C under 30 bar. After 1 h, the autoclave was cooled
to 7 °C and then depressurised over a period of 1 h. Heptane (200
µL), which serves as internal reference for the GC analysis, was
then added to the reaction mixture. The liquid phase was analysed
with a VARIAN 3900 gas chromatograph equipped with a WCOT
fused silica column (25 m, 0.32 mm inside diameter, 0.25 mm film
thickness).
Crystal Structure Determination of 2·2CH2Cl2: Single crystals of 2
suitable for X-ray diffraction analysis were obtained by slow dif-
fusion of hexane into a CH2Cl2 solution of the complex. Data were
collected with a Nonius KappaCCD diffractometer (graphite-mon-
˚
ochromated Mo-Kα radiation, λ ϭ 0.71073 A). The structure was
solved by direct methods using the SHELXS-97 program and re-
fined by full-matrix least-squares techniques (SHELXL-97) on
F2.[39] Hydrogen atoms were located using the geometric method.
The crystal data and structural refinement details are listed in
Table 3. The compound was found to crystallise with two molecules
of dichloromethane, one of them lying inside the cavity.
CCDC-234357 contains the supplementary crystallographic data
for this structure. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; Fax: ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Acknowledgments
`
We thank the Ministere de l’Education Nationale et de la
Recherche Scientifique for a grant to P. K.
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Coordination Chemistry of Large Diphosphanes
FULL PAPER
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[21]
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Early View Article
Published Online October 13, 2004
Eur. J. Inorg. Chem. 2004, 4602Ϫ4607
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4607