New Diphosphane Ligands Based on Bisphenol A Backbones - Synthesis and Coordination Chemistry

Article abstract of DOI:10.1002/ejic.200300419

A series of easily accessible diphosphane compounds 1-4, based on bisphenol A derived backbones, has been prepared. A straightforward two-step synthetic route has been employed to obtain these new ligands in good yields from cheap starting materials. Mole

Full text of DOI:10.1002/ejic.200300419

FULL PAPER
New Diphosphane Ligands Based on Bisphenol A Backbones ؊ Synthesis and
Coordination Chemistry
Jarl Ivar van der Vlugt,[a] Michiel M. P. Grutters,[a] Allison M. Mills,[b] Huub Kooijman,[b]
Anthony L. Spek,[b] and Dieter Vogt*[a]
Keywords: Ligand design / Phosphanes / Coordination modes / Structure elucidation / Transition metals
A series of easily accessible diphosphane compounds 1−4,
palladium, platinum, and rhodium precursors has been
based on bisphenol A derived backbones, has been pre- studied by NMR spectroscopy as well as X-ray crystallo-
pared. A straightforward two-step synthetic route has been
employed to obtain these new ligands in good yields from
graphy. The molecular structures of the face-to-face dimeric
species [{PdCl(CH3)(2)}2] (6), [{PtCl2(2)}2] (7), and
cheap starting materials. Molecular structures for both com- [{RhCl(CO)(2)}2] (8) are described in detail.
pound 2 and its oxidized form (5·H2O) have been determined
and are discussed in detail. The coordination of ligand 2 to
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
uct with methanol afforded the pure compounds in overall
yields of 40Ϫ50%. Using this method, we obtained com-
pounds 1Ϫ3 based on derivatives of the Bisphenol A back-
bone. Furthermore, the silicon derivative 4 was synthesized
in good yield starting from 4-bromoanisole and dichlorodi-
methylsilane via a modified two-step route. Compounds
The coordination chemistry of diphosphane ligands with
a variety of transition metals has been widely studied and
several types of coordination modes have been established
over the years.[1,2] Numerous families of novel ligands have
been synthesized,[3] with emphasis on cis-chelation to form
monomeric metal complexes. As well as designing ligands
based on desired behaviour towards transition metals and
the catalytic activity of the resultant systems, the approach
of modular design and availability from cheap resources has
gained significant importance.
We have chosen Bisphenol A as a somewhat neglected yet
promising starting material for the synthesis of a new ligand
class.[4,5] A wide range of these bisphenols is commercially
available at low price since they are used as components in
epoxy resins. Generic structures are easily available by sim-
ple acid catalyzed condensation of a ketone with two mol-
ecules of a phenol.[6] Based on these versatile compounds
we employed a straightforward two-step synthetic route to
novel P-containing compounds (Scheme 1).
1
1Ϫ4 were characterized by H, 13C, and 31P NMR spec-
troscopy, as well as by elemental analysis. We have pre-
viously reported this synthetic route, focussing on the syn-
thesis and catalytic applicability of a ligand derived from
1,2-diphenylbenzene as the backbone.[5]
We were able to obtain single crystals, suitable for X-ray
analysis, for compounds 1Ϫ3, by recrystallization of the
pure solids from hot 1-propanol or hot acetonitrile. Only
the molecular structure of compound 2 is depicted in Fig-
ure 1, while selected bond lengths and bond angles for all
three compounds are summarized in Table 1.
Because of the rotational freedom of the aromatic rings
in the backbone, the diphenylphosphane groups are not
constrained to any particular mutual orientation. Com-
pound 2 shows approximate C2 symmetry. The bond dis-
tances between the ipso-carbons of the backbone with the
In the first step, the phenol groups were protected by
methylation with iodomethane. Subsequently, selective or-
tho-lithiation of both phenyl rings was followed by reaction
with the phosphane source ClPPh2. Filtration and evapor-
ation of the solvent followed by washing of the crude prod-
1
3
˚
phosphorus atoms are normal at around 1.84 A [P ϪC
2
9
˚
˚
1.840(2) A and P ϪC 1.845(2) A]. The central-carbon
(C15) of the backbone is clearly tetrahedrally surrounded.
The through-space P1ϪO1 and P2ϪO2 distances are around
˚
2.8Ϫ2.9 A. The intramolecular PϪP distance is 9.7664(8)
[a]
˚
Schuit Institute of Catalysis, Laboratory of Homogeneous
A.
Catalysis, Eindhoven University of Technology,
P. O. Box 513, 5600 MB Eindhoven, The Netherlands
Fax: (internat.) ϩ 31-40-2455054
To obtain the corresponding diphosphane oxide, we re-
acted compound 2 with hydrogen peroxide to yield com-
pound 5. In the 31P NMR spectrum a singlet was observed
at δ ϭ 27.7 ppm which is a typical value for a phosphane
oxide.[7] We were able to obtain single crystals, suitable for
E-mail: d.vogt@tue.nl
[b]
Laboratory for Crystal and Structural Chemistry, Department
of Chemistry, Utrecht University,
Padualaan 8, 3584 CH, Utrecht, The Netherlands
Eur. J. Inorg. Chem. 2003, 4361Ϫ4369
DOI: 10.1002/ejic.200300419
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J. I. van der Vlugt, M. M. P. Grutters, A. M. Mills, H. Kooijman, A. L. Spek, D. Vogt
FULL PAPER
Scheme 1. Synthetic route to BPphos
Figure 1. Molecular structure of compound 2
pound 5 and the hydrogen atoms of the water molecule.[8]
Table 1. Selected bond lengths and angles for compounds 1Ϫ3
The OϪH···O(P) contacts are almost equivalent with
H ϪO(P) bond lengths of 1.99(5) A (H ϪO ) and 2.01(5)
#
#
3
˚
1
2
3
#
4
˚
A (H ϪO ), which are much smaller than the calculated
˚
Bond lengths [A]
5
˚
sum of the van der Waals radii of 2.72 A. The O ϪO(P)
P1ϪC3
1.8484(15)
1.8428(16)
1.429(2)
1.374(2)
1.429(3)
1.372(2)
9.8510(6)
1.840(2)
1.845(2)
1.431(3)
1.370(2)
1.425(3)
1.372(2)
9.7664(8)
1.8354(16)
1.8385(17)
1.413(3)
1.375(2)
1.424(2)
1.376(2)
6.7749(6)
3
5
4
5
˚
˚
distances are 2.835(7) A (O ϪO ) and 2.822(7) A (O ϪO )
and the O5ϪH#ϪO(P) angles are 166(5)° (P1) and 168(6)°
(P2), respectively. Furthermore, the orientation of the two
phosphorus atoms is dramatically altered relative to the
structure of the free ligand (vide supra). Due to the tem-
plate effect of the water molecule, both P-atoms are located
on the same side of the molecule with the oxygen atoms
pointing towards one another. This leads to a decreased
P2ϪC9
O1ϪC1
O1ϪC4
O2ϪC2
O2ϪC10
P1ϪP2
Angles [°]
C1ϪO1ϪC4
C2ϪO2ϪC10
P1ϪC3ϪC4
P2ϪC9ϪC10
C7ϪC15ϪC13
117.64(13)
118.26(14)
118.25(11)
117.17(13)
111.30(13)
117.52(17)
117.86(16)
118.01(14)
118.72(15)
106.96(14)
118.25(14)
117.61(14)
116.89(12)
116.99(13)
110.23(13)
1
2
˚
P ϪP distance of 6.579(2) A. The bond lengths between
the phosphorus and carbon atoms of the ligand backbone
(P1ϪC3 and P2ϪC9) are slightly shorter than the corre-
sponding distances in compound 2, due to a decrease of
electron density on the phosphorus atoms in the oxidized
state. The PϪO bond lengths found for both phosphane
X-ray analysis, from a THF solution. The molecular struc-
ture is depicted in Figure 2, with selected bond lengths and
angles listed in Table 2.
The structure of compound 5 represents the diphosphane
oxide of 2 but with an additional molecule of water present.
There is hydrogen-bonding between the oxo groups of com-
1
3
˚
˚
oxide moieties, 1.491(4) A (P ϪO ) and 1.492(5) A
(P2ϪO4), are similar to those found in triphenylphosphane
oxide hemihydrate[8] and tris(p-tolyl)phosphane oxide[9] but
slightly lower in comparison with the mono oxide of
4362
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Eur. J. Inorg. Chem. 2003, 4361Ϫ4369

New Diphosphane Ligands Based on Bisphenol A Backbones
FULL PAPER
Figure 2. Crystal structure of compound 5
trans-coordinated PdCl2 complex using 3,3Ј-oxybis[(di-
phenylphosphanyl)methyl]benzene, which is structurally re-
lated to compounds 1Ϫ4.[13]
Table 2. Selected bond lengths and angles for compound 5·H2O
˚
Bond lengths [A]
Angles [°]
From the reaction of 2 with [PdClCH3(cod)] as a starting
material, only a singlet at δ ϭ 25.0 ppm was observed in
the 31P NMR spectrum. In the 1H NMR spectrum, a broad
triplet was present at δ ϭ Ϫ0.05 ppm and a singlet at δ ϭ
3.8 ppm was seen in the 13C NMR spectrum. These obser-
vations are clear indications that a trans-coordinated species
is present, either monomeric or dimeric. For monomeric
trans-coordinated [PdClCH3(Xantphos)] complexes, Zuide-
veld et al. have reported proton methyl signals at around
δ ϭ Ϫ0.2 ppm.[14] Upon slow evaporation of the deuterated
solvent, yellow block-shaped single crystals, suitable for X-
ray analysis, were obtained for this compound. The crystal-
lographic study undertaken, indicated formation of the di-
meric macrocyclic complex 6 which did indeed display a
trans-coordination for each of the two phosphorus atoms
and two bridging palladium atoms. The molecular structure
of complex 6 is depicted in Figure 3, while Table 3 contains
selected bond lengths and bond angles.
P1ϪC3
P2ϪC9
O1ϪC1
O1ϪC4
O2ϪC2
O2ϪC10
P1ϪO3
P2ϪO4
P1ϪP2
1.810(7)
1.803(9)
1.427(9)
1.378(8)
1.416(9)
1.383(9)
1.491(4)
1.492(5)
6.579(2)
C1ϪO1ϪC4
117.4(6)
118.9(6)
125.4(5)
125.6(5)
105.1(5)
110.1(3)
109.9(3)
C2ϪO2ϪC10
P1ϪC3ϪC4
P2ϪC9ϪC10
C7ϪC15ϪC13
O3ϪP1ϪC3
O4ϪP2ϪC9
BINAP.[10] We are currently investigating the inclusion of
other molecules capable of forming hydrogen bonds in or-
der to form three-dimensional networks. The coordination
behaviour of the phosphane oxide, which is still a weakly
coordinating group,[11] has also been studied.
We were interested in the coordination of the novel di-
phosphane compounds to various transition metals and, in
particular, whether the chelate ring size of 9 atoms (includ-
The complex is centrosymmetric and the geometry
ing the two P-atoms) would have implications for the mode around the palladium atoms is distorted square planar, as
of coordination and if bidentate mononuclear complexes indicated by the corresponding angles listed in Table 2. The
would be formed.
P1ϪPdϪP2 angle is 172.94(3)°, while the C1ϪPd1ϪCl1 an-
˚
Rauchfuss et al. have already investigated the monophos- gle is 171.64(13)°. The PdϪP bond lengths of 2.3250(9) A
1
2
˚
phane (diphenylphosphanyl)anisole and they concluded (PdϪP ) and 2.3248(9) A (PdϪP ) are typical for triaryl-
that coordination to a metal, such as palladium and plati- phosphanes[15,16] as are the lengths of the palladium to
num, took place only through the phosphorus.[12] In order chlorine and palladium to methyl bonds.[17] The P1ϪP2a
˚
to study the coordination chemistry of the new family of distance was found to be 7.4470(13) A. Other binuclear pal-
BPphos ligands to Pd, Pt, and Rh, we used ligand 2 as ladium complexes with a face-to-face structure that have
a representative example. Marty et al. have reported some been described in literature most often have two chlorine
experimental evidence for the formation of a monomeric, ligands coordinated to the metal center instead of one
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J. I. van der Vlugt, M. M. P. Grutters, A. M. Mills, H. Kooijman, A. L. Spek, D. Vogt
FULL PAPER
195Pt-satellites, and a coupling constant JPtϪP of 2705 Hz.
This clearly indicates a trans-coordination of two phos-
phorus atoms.[21] These block-shaped crystals turned out to
be suitable for X-ray analysis. The molecular structure for
complex 7 is depicted in Figure 4. Selected bond lengths
and bond angles are listed in Table 4.
Figure 3. X-ray structure of complex 6
Table 3. Selected bond lengths and angles for complex 6,
trans,trans-[{PdCl(CH3)(µ-2)}2]
˚
Bond lengths [A]
Angles [°]
Pd1ϪP1
Pd1ϪP2
Pd1ϪCl1
Pd1ϪC1
P1ϪC4
2.3250(9)
2.3248(9)
2.4330(10)
2.075(4)
1.836(3)
1.830(3)
P1ϪPd1ϪP2
172.94(3)
171.64(13)
88.18(3)
88.41(3)
92.30(9)
90.17(9)
105.2(3)
C1ϪPd1ϪCl1
P1ϪPd1ϪCl1
P2ϪPd1ϪCl1
P1ϪPd1ϪC1
P2ϪPd1ϪC1
C8ϪC16ϪC14a
Figure 4. X-ray structure of complex 7
P2ϪC10
P1ϪP2a
Pd1ϪPd1a
Table 4. Selected bond lengths and angles for complex 7,
trans,trans-[{PtCl2(µ-2)2}2]
7.4470(13)
7.4972(4)
˚
Bond lengths [A]
Angles [°]
Pt1ϪP1
Pt1ϪP2
Pt1ϪCl1
Pt1ϪCl2
P1ϪC3
2.320(2)
2.315(2)
2.294(2)
2.3270(18)
1.835(7)
1.827(7)
8.627(3)
8.6391(5)
P1ϪPt1ϪP2
176.78(7)
92.33(8)
90.09(7)
171.77(7)
88.80(7)
88.38(7)
108.9(7)
chlorine and one methyl ligand.[18,19] Davies et al. have de-
scribed the face-to-face dimer [Pd2Cl2(CH2NO2)(µ-
dmpm)2] (dmpm ϭ Me2PCH2PMe2). The bond lengths be-
tween the palladium and the chlorine or the carbon atom
of the nitromethyl group turned out to be slightly shorter
than in the case of complex 6, due to the electronic with-
drawing effect of the nitro unit.[20] Only very recently the
group of James published the synthesis and structural
characterization of the Pd2Cl4 derivative of dmpm.[20b]
P1ϪPt1ϪCl1
P1ϪPt1ϪCl2
Cl1ϪPt1ϪCl2
P2ϪPt1ϪCl1
P2ϪPt1ϪCl2
C7ϪC15ϪC13a
P2ϪC9
P1ϪP2a
Pt1ϪPt1a
Like the palladium complex 6, the molecular structure of
Kemmitt and co-workers quite recently reported various di- complex 7 also turned out to be dimeric and centrosym-
meric palladium-diphosphane complexes with a chlorine metric. The geometry around the platinum atoms is dis-
and a phenyl group attached to the palladium atoms.[16]
torted square planar, with a P1ϪPtϪP2 angle of 176.78(7)°
In order to verify if the formation of face-to-face dimeric and a Cl1ϪPtϪCl2 angle of 171.77(7)°. The geometry
complexes is always favoured, regardless of the transition around the central atom C15 of the ligand backbone is
metal, we decided to study the complexation of ligand 2 nearly perfectly tetrahedral, as indicated by the angle of
with
a
platinum precursor. After reaction with 108.9(7)° for both phenyl rings. Interestingly, the P1ϪP2a
˚
[PtCl2(CH3CN)2], an off-white solid was obtained. After distance of 8.627(3) A is larger than in the palladium-dimer
dissolving this compound in acetone and slow evaporation 6. The PϪPt and ClϪPt bond lengths are in their expected
of the solvent, one product could be isolated as yellow sin- ranges, compared with similar structures previously re-
gle crystals in good yield. The 31P NMR spectrum of this ported.[22,23] Wood et al. showed that the reaction of 2,6-
compound showed a singlet at δ ϭ 15.8 ppm, flanked by bis(diphenylphosphanyl)pyridine with PtCl2 yielded a cis-
4364
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New Diphosphane Ligands Based on Bisphenol A Backbones
FULL PAPER
dimer. When the chlorine-ligands were substituted for iod-
ine-ligands, however, the phosphorus atoms were coordi-
nated in a trans-fashion.[24]
To further understand the formation of these face-to-face
dimers, we chose the rhodium precursor [{Rh(µ-
Cl)(CO)2}2]. Complexes prepared from this metal source
normally exhibit a trans-coordination for the phosphorus
atoms. After reaction of this rhodium species with ligand 2,
a doublet was observed in the 31P NMR spectrum at δ ϭ
23.7 ppm, with a coupling constant JRhϪP of 128.3 Hz. This
value is typical of those seen in rhodium diphenylphos-
phane complexes.[25] In the carbonyl region of the IR spec-
trum (ATR-mode) obtained from the solid product, the
CO-stretching vibration was present at νCO ϭ 1976 cmϪ1
.
This is in good agreement with the value of νCO ϭ 1974
cmϪ1 reported for [RhCl(CO){P(o-An)Ph2}] (An ϭ ani-
sole).[26] Compared with the value of νCO ϭ 1982 cmϪ1
found for [RhCl(CO){PPh2(C6F5)}][27] and νCO ϭ 1980
cmϪ1 for [Rh(Cl)(CO)(PPh3)2][28], the value found for our
Rh complex is slightly low. Note: Moloy and Petersen have
touched upon the discrepancy arising in literature with re-
spect
to
the
CO
stretching
frequency
for
[Rh(Cl)(CO)(PPh3)2]. Their own experiments showed a sin-
gle band at νCO ϭ 1965 cmϪ1 in CH2Cl2.[29] The value of
1976 cmϪ1 demonstrates that the ligands from the BPphos
family are slightly more basic than the aforementioned two
ligand systems. However the value is signifcantly higher
than that found for Rh(Cl)(CO) complexes with alkyldiaryl-
phosphanes such as those described by Zhang et al.[30] and
by the group of Dilworth (ν ϭ 1957 cmϪ1).[31]
By slow diffusion of acetonitrile into a dichloromethane
solution of the compound, single crystals could be grown
that were suitable for an X-ray crystallographic study. The
molecular structure for centrosymmetric complex 8 is
shown in Figure 5. Similar to the Pd and Pt complexes, a
face-to-face dimeric structure can be observed. Selected
bond lengths and bond angles are listed in Table 5.
Figure 5. X-ray structure of complex 8
Table 5. Selected bond lengths and angles for complex 8,
trans,trans-[{RhCl(CO)(µ-2)2}2]
˚
Bond lengths [A]
Angles [°]
P1ϪRh1ϪP2
Rh1ϪP1
Rh1ϪP2
Rh1ϪCl1
Rh1ϪC1
C1ϪO1
2.3153(5)
2.3345(6)
2.3795(5)
1.810(2)
171.01(3)
87.85(3)
90.36(3)
176.99(7)
89.80(7)
92.24(7)
177.33(18)
116.75(6)
110.19(15)
P1ϪRh1ϪCl1
P2ϪRh1ϪCl1
Cl1ϪRh1ϪC1
P1ϪRh1ϪC1
P2ϪRh1ϪC1
Rh1ϪC1ϪO1
Rh1ϪP1ϪC4
C8ϪC16ϪC14a
1.145(2)
P1ϪC4
1.8349(17)
1.8352(18)
8.8150(12)
9.0005(11)
P2ϪC10
P1ϪP2a
Rh1ϪRh1a
The geometry around the rhodium atoms is distorted
square planar, with a PϪRhϪP angle of 171.01(3)° and a
ClϪRhϪC(O) angle of 176.99(7)°. These distances are in
the expected range with an average RhϪP bond length of
structural differences between compound 2 and its oxidised
form, 5. In the structure of the latter compound, water acts
as a template orientating both phosphorus-atoms to the
same side of the molecule in the same direction. Com-
plexation studies undertaken with ligand 2 yielded face-to-
face dimeric macrocycles with palladium, platinum and
rhodium, as was shown by NMR spectroscopy as well as
X-ray crystallography.
We are currently investigating the options available for
modifying the ligand backbone to further control and en-
force a certain orientation of the phosphane-moieties as
well as the modification of these ligands in order to gain
access to chelating variants.
˚
2.32 A. The RhϪCl and RhϪC(O) bond lengths are
˚
˚
2.3795(5) A and 1.810(2) A, respectively. The CϪO distance
[30Ϫ34]
˚
is typical at 1.145(2) A.
8.8150(12) A as well as the corresponding RhϪRh distance
of 9.0005(11) A are in the range found for the palladium
The P1ϪP2a distance of
˚
˚
and platinum complexes.
Many trans-[RhCl(CO)] complexes with (di)phosphane
ligands have been described in the literature, yet most of
these systems are solely mononuclear. Relatively few ex-
amples are known where a dimeric compound has been
formed exclusively and subsequently structurally charac-
terized by X-ray crystallography.[35Ϫ39]
In summary, we have described the easy synthesis of a
new class of diphosphane ligands based on commercially
available, cheap raw materials derived from Bisphenol A
and in good overall yields. In addition to NMR spec-
Experimental Section
Chemicals were purchased from Aldrich, Acros, and Merck and
troscopy, X-ray crystallography has been used to study the used as received. All preparations were carried out under an argon
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J. I. van der Vlugt, M. M. P. Grutters, A. M. Mills, H. Kooijman, A. L. Spek, D. Vogt
FULL PAPER
atmosphere using standard Schlenk techniques. Solvents were dis-
tilled from sodium/benzophenone (THF, diethyl ether, toluene, hex-
anes, and ethanol) or calcium hydride (CH2Cl2 and CDCl3) prior
was dissolved in THF (100 mL) and the solution was cooled to
Ϫ78 °C whereupon nBuLi (2.5  solution in hexanes) (12.4 mL,
31.0 mmol) was added dropwise by syringe. The reaction mixture
to use. [PdCl2(cod)],[40] [PdClMe(cod)][41] and [PtCl2(cod)][42] were was stirred for 1 h followed by addition of SiCl2(CH3)2 (2.0 g,
synthesized according to literature procedures. All glassware was
dried by heating under vacuum. The NMR spectra were recorded
on a Varian Mercury 400 spectrometer (1H, 13C{1H}, 31P{1H}).
Chemical shifts are given in ppm referenced to the deuterated sol-
vent (1H, 13C{1H}) or 85% H3PO4 (31P{1H}).
31.0 mmol) by syringe. The reaction mixture was allowed to warm
up to room temp. and stirring was continued for about 10 h. Sol-
vents were removed in vacuo and the crude product was dissolved
in CH2Cl2 (30 mL). Washing with distilled water (40 mL) afforded
a turbid white organic layer. The organic phase was separated and
the solvent removed in vacuo to leave a yellow oil. Upon addition
of hexanes (25 mL), a brown precipitate was formed. The solution
was isolated and dried with MgSO4. After filtration and subsequent
removal of solvent, an off-white solid was obtained. Yield 71%
(3.00 g, 22.0 mmol). 1H NMR (400 MHz, CDCl3, 300 K, ppm):
δ ϭ 0.54 [s, 6 H, Si(CH3)], 3.83 (s, 6 H, OCH3), 6.93 (d, 1J ϭ
8.8 Hz, 4 H, H2), 7.48 (d, 1J ϭ 8.8 Hz, 4 H, H1). 13C NMR
(100 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ2.0, 55.0, 113.5, 129.4,
135.6, 155.0. 160.4.
2,2-Bis(4-methoxyphenyl)propane (A): This is a modification of the
literature procedure.[43] To a solution of Bisphenol A [2,2Ј-bis(4-
hydroxyphenyl)propane] (11.48 g, 0.050 mol) in acetone (120 mL)
were added K2CO3 (27.69 g, 0.20 mol) and CH3I (21.69 g, 0.15
mol) as well as NBu4I (0.88 g, 2.38 mmol). The heterogeneous mix-
ture was stirred for 16 h under reflux. The suspension was filtered
through celite and poured into a mixture of diethyl ether (100 mL)
and a 15 w% aqueous KOH solution (100 mL). The organic phase
was further washed with saturated brine (100 mL) and water
(50 mL) after which MgSO4 was added and the organic phase
stirred for about 10 h. After filtration through Celite the solvent
was removed in vacuo and ethanol (40 mL) was added to the re-
maining oil. After stirring, the ethanol was removed in vacuo to
yield a pure off-white powder (9.44 g, 36.8 mmol) (73%). 1H NMR
(400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.65 (s, 6 H, CCH3), 3.79 (s,
6 H, OCH3), 6.81 (d, 1J ϭ 8.8 Hz, 4 H, m-H2), 7.15 (d, 1J ϭ 8.8 Hz,
4 H, o-H1) (Numbering scheme see Figure 6). 13C NMR (100 MHz,
CDCl3, 300 K, ppm): δ ϭ 31.1, 41.6, 55.2, 113.2, 127.7, 143.1,
157.4.
2,2-Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]propane (1):
TMEDA (12.95 g, 0.11 mol) was added to nBuLi (2.5  solution
in hexanes) (44.6 mL, 0.11 mol). At Ϫ15 °C a solution of A
(13.29 g, 0.052 mol) in diethyl ether (75 mL) was added dropwise
over a period of 1.5 h. The mixture was allowed to slowly warm
up to room temp. and was stirred for about 10 h to yield a yellow
suspension. At 0 °C ClPPh2 (24.6 g, 0.11 mol) in hexanes (30 mL)
was added dropwise over a period of 1 h. Solvents were removed
in vacuo and CH2Cl2 (60 mL) was added together with saturated
brine (50 mL). The organic phase was separated and dried with
MgSO4. After filtration through celite, the solvents were removed
in vacuo to yield a pink oil that solidified on standing for about
10 h at room temp. under argon. Ethanol (40 mL) was added to
give an orange solution and a white precipitate. The solid was
washed with ethanol, filtered, and dried. Yield 54% (17.46 g,
1
28.1 mmol). H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.24
(s, 6 H, CCH3), 3.73 (s, 6 H, OCH3), 6.40 (dd, 1J ϭ 5.2, 2J ϭ
Figure 6. Numbering scheme for protons H1 and H2 of com-
pounds AϪD
1
2
2.4 Hz, 2 H, H1), 6.73 (dd, J ϭ 8.8, J ϭ 4.8 Hz, 2 H, H2), 7.04
(dd, 1J ϭ 8.8, 2J ϭ 2 Hz, 2 H, H3), 7.24 (m, 20 H, PPh2) (Number-
ing scheme see Figure 7). 13C NMR (100 MHz, CDCl3, 300 K,
ppm): δ ϭ 30.3 [C(CH3)2], 41.6 [C(CH3)2], 55.7 (OCH3), 109.5,
124.3, 128.2 (d, JP,C ϭ 6.8 Hz), 128.3, 128.4, 132.4, 133.7 (d, JP,C ϭ
1,1-Bis(4-methoxyphenyl)cyclohexane (B): This is a modification of
the literature procedure.[44] Starting from Bisphenol Z [1,1-bis(4-
hydroxyphenyl)cyclohexane] (28.8 g, 0.11 mol), compound B was
obtained as a white crystalline solid, using the same procedure as
described for A. Yield 83.5% (27.7 g, 93.5 mmol). 1H NMR
(400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.55 (m, 6 H, m-,p-CH2, c-
C6), 2.23 (m, 4 H, o-CH2, c-C6), 3.77 (s, 6 H, OCH3), 6.81 (d, 1J ϭ
8.8 Hz, 4 H, m-H2), 7.18 (d, 1J ϭ 8.8 Hz, 4 H, o-H1). 13C NMR
(100 MHz, CDCl3, 300 K, ppm): δ ϭ 22.9, 26.4, 37.4, 45.0, 55.1,
113.4, 128.0, 141.0, 157.1.
19.8 Hz), 136.9 (d, JP,C ϭ 10.7 Hz), 143.0, 159.0 (d, JP,C
ϭ
14.5 Hz). 31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ
Ϫ14.8 (s). C41H38O2P2: calcd. C 78.83, H 6.13; P, 9.92; found C
78.65, H 6.08; P, 9.98.
2,2-Bis(4-methoxyphenyl)ethylbenzene (C): This is a modification of
the literature procedure.[45] Starting from Bisphenol AP {[2,2-bis(4-
hydroxyphenyl)ethyl]benzene} (20.0 g, 68.9 mmol), compound C
was obtained as a pure off-white powder, using the same procedure
as described for A. Yield 64% (13.92 g, 43.7 mmol). 1H NMR
(400 MHz, CDCl3, 300 K, ppm): δ ϭ 2.14 [s, 6 H, C(CH3)], 3.79,
(s, 6 H, OCH3), 6.79 (d, 1J ϭ 8.8 Hz, 4 H, H2), 7.00 (d, 1J ϭ 8.8 Hz,
4 H, H1), 7.09 (m, 2 H, o-CH, Ph), 7.20 (m, 1 H, p-CH, Ph), 7.26
(m, 2 H, m-CH, Ph). 13C NMR (100 MHz, CDCl3, 300 K, ppm):
δ ϭ 30.7, 55.2, 113.1, 125.8, 127.8, 128.6, 129.7, 141.5, 157.6.
Figure 7. Numbering scheme for protons H1, H2, and H3 of com-
pounds 1Ϫ8
1,1-Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]cyclohexane
(2):
Starting from B (4.99 g, 0.017 mol), compound 2 was obtained as
a white powder using the same procedure as described for com-
pound 1. Yield 56% (6.34 g, 9.4 mmol). 1H NMR (400 MHz,
CDCl3, 300 K, ppm): δ ϭ 1.23 (m, 6 H, m,p-CH2, c-C6), 1.73 (m,
Bis(4-methoxyphenyl)dimethylsilane (D): This is a modification of
the literature procedure.[46] 4-Bromoanisole (5.79 g, 0.031 mmol)
4366
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 4361Ϫ4369

New Diphosphane Ligands Based on Bisphenol A Backbones
FULL PAPER
obtained by slow evaporation of the solvent from the NMR solu-
1
2
4 H, o-CH2, c-C6), 3.71 (s, 6 H, OCH3), 6.47 (dd, J ϭ 5.6, J ϭ
2.4 Hz, 2 H, H1), 6.72 (dd, 1J ϭ 8.8, 2J ϭ 4.8 Hz, 2 H, Ar-H2), tion. 1H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ0.05 (t, 6
6.99 (dd, J ϭ 8.8, J ϭ 2.4 Hz, 2 H, H3), 7.24 (m, 20 H, PPh2). H, PdCH3), 1.26 (br. s, 12 H, m,p-CH2, c-C6), 1.80 (br. s, 8 H, o-
1
2
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 22.7, 26.2, 37.0,
45.2, 55.6, 109.8, 125.7, 128.2, 128.3 (d, JP,C ϭ 13.0 Hz), 128.8,
CH2, c-C6), 3.61 (s, 12 H, OCH3), 6.71 (d, J ϭ 8.0 Hz, 4 H, H3),
1
7.04 (d, J ϭ 8.0 Hz, 8 H, H1, H2), 7.30 (m, 24 H, PPh2), 7.71 (br.
1
132.9, 133.7 (d, JP,C ϭ 19.8 Hz), 137.0, 140.9, 159.0 (d, JP,C
Ϫ15.2 (s). C44H42O2P2: calcd. C 79.50, H 6.37; P, 9.32; found C
79.39, H 6.39; P, 9.31
ϭ
s, 16 H, PPh2). 13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ
3.8, 22.8, 26.3, 37.1, 45.1, 55.5, 110.8, 119.0, 119.2, 127.5, 129.2,
130.9, 131.6, 133.3, 135.0, 140.4, 157.9. 31P{1H} NMR (162 MHz,
CDCl3, 300 K, ppm): δ ϭ 25.0 (s). C90H90Cl2O4P4Pd2: calcd. C
65.78, H 5.52; found C 65.60, H 5.46.
2,2-Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]ethylbenzene (3):
Starting from C (12.4 g, 38.9 mmol), compound 3 was obtained as
a white powder using the same procedure as described for com-
pound 1. Yield 61% (16.5 g, 23.7 mmol). 1H NMR (400 MHz,
CDCl3, 300 K, ppm): δ ϭ 1.74 (s, 3 H, CCH3), 3.72 (s, 6 H, OCH3),
trans,trans-[PtCl2-2]2, Complex 7: PtCl2 (170.3 mg, 640.5 µmol) was
heated to reflux in acetonitrile (10 mL) until the solid had com-
pletely dissolved. Ligand 2 (425.8 mg, 640.5 µmol) was added and
the mixture stirred under reflux for about 10 h. After cooling to
room temp., the solvent was evaporated in vacuo to leave a yellow
powder. Single crystals were obtained from acetone, by slow evap-
1
6.33 (dd, 1J ϭ 5.6, 2J ϭ 2.4 Hz, 2 H, H1), 6.67 (dd, J ϭ 8.8, 2J ϭ
4.8 Hz, 2 H, H2), 6.81 (m, 2 H, o-CH, Ph), 6.91 (dd, 1J ϭ 8.8, 2J ϭ
2.4 Hz, 2 H, H3), 7.07 (m, 3 H, m-,p-CH, Ph), 7.18 (m, 20 H, PPh2).
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 30.0, 51.2, 55.6,
1
oration of the solvent. H NMR (400 MHz, CDCl3, 300 K, ppm):
δ ϭ 1.23 (m, 12 H, m,p-CH2, c-C6), 1.71 (br. s, 8 H, o-CH2, c-C6),
109.3, 124.2 (d, JP,C ϭ 13.0 Hz), 125.5, 127.6, 128.2 (d, JP,C
6.8 Hz), 128.3 (d, JP,C ϭ 3.1 Hz), 130.2, 133.6 (d, JP,C ϭ 19.8 Hz),
ϭ
1
3.63 (s, 12 H, OCH3), 6.67 (d, J ϭ 8.0 Hz,4 H, H1), 7.00 (br. s, 4
1
H, H2), 7.09 (d, J ϭ 8.8 Hz, 4 H, H3), 7.37 (br. m, 24 H, PPh2),
134.1, 136.7 (d, JP,C ϭ 10.7 Hz), 141.3, 149.0, 159.1 (d, JP,C
ϭ
14.5 Hz). 31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ
Ϫ15.3 (s). C46H40O2P2: calcd. C 80.45, H 5.87; P, 9.02; found C
80.52, H 5.76; P, 9.05.
7.73 (q, 1J ϭ 5.6 Hz, 16 H, PPh2). 31P{1H} NMR (162 MHz,
CDCl3, 300 K, ppm):
δ ϭ 15.8 (s, JPtϪP ϭ 2705 Hz).
C88H84Cl4O4P4Pt2: calcd. C 56.78, H 4.55; found C 56.65, H 4.45.
Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]dimethylsilane
(4):
trans,trans-RhCl(CO)-2, Complex 8: [RhCl(CO)2]2 (170.3 mg, 640.5
µmol) and ligand 2 (425.8 mg, 640.5 µmol) were dissolved in
CH2Cl2 (10 mL) and the mixture was stirred for 2 h. Evaporation
of the solvent in vacuo yielded a yellow solid. Single crystals were
obtained by slow diffusion of CH3CN into a CH2Cl2 solution of
Starting from D (3.00 g, 0.011 mol), compound 4 was obtained as
a white powder using the same procedure as described for com-
pound 1. Yield 65% (4.58 g, 7.20 mmol). 1H NMR (400 MHz,
CDCl3, 300 K, ppm): δ ϭ 0.09 [s, 6 H, Si(CH3)], 3.75 (s, 6 H,
1
2
1
OCH3), 6.69 (dd, J ϭ 8.0, J ϭ 4.4 Hz, 2 H, H1), 6.81 (dd, J ϭ
1
the solid. H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.20 (br.
8.0, J ϭ 4.4 Hz, 4 H, H2, H3), 7.28 (m, 20 H, PPh2). 13C NMR
2
s, 12 H, m,p-CH2, c-C6), 1.64 (br. s, 8 H, o-CH2, c-C6), 3.61 (s, 12
H, OCH3), 6.65 (d, 1J ϭ 8.8 Hz, 4 H), 6.87 (br. s, 4 H), 7.00 (d,
(100 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ2.6, 55.5, 109.7, 124.7,
128.2 (d, JP,C ϭ 6.8 Hz), 128.5, 129.5, 133.8 (d, JP,C ϭ 19.8 Hz),
136.3, 136.7 (d, JP,C ϭ 9.9 Hz), 139.5, 161.9 (d, JP,C ϭ 15.9 Hz).
31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ16.1 (s).
C40H38O2P2Si: calcd. C 74.98, H 5.98; P, 9.67; found C 75.06, H
5.93; P, 9.63.
1
1
1J ϭ 6.4 Hz, 4 H), 7.38 (t, J ϭ 7.2 Hz, 16 H, PPh2), 7.46 (q, J ϭ
7.2 Hz, 8 H, PPh2), 7.82 (br. s, 16 H, PPh2). 31P{1H} NMR
(162 MHz, CDCl3, 300 K, ppm): δ ϭ 23.7 (d, JRhϪP ϭ 128 Hz).
IR (ATR mode, solid, carbonyl region, cmϪ1): ν
˜ ϭ 1976 (RhCO).
C90H84Cl2O6P4Rh2: calcd. C 65.03, H 5.09; found C 64.88, H 4.96.
Bis(2,2Ј-methoxy-5,5Ј-cyclohexyl)diphenylphosphane Oxide (5): Li-
gand 2 (0.65 g, 0.98 mmol) was dissolved in CH2Cl2 (25 mL) and
H2O2 (30 wt% aqueous solution) (0.20 mL, 1.96 mmol) in H2O
(20 mL) was added dropwise at 0 °C after which the two-phase
system was stirred for about 10 h at room temp. The organic layer
was washed with 0.1  NaOH solution (20 mL) and water (20 mL).
After drying with MgSO4 and subsequent filtration, the solvent
was removed in vacuo to leave a white powder. Yield 85% (0.58 g,
Molecular Structures of 1؊3 and 5؊8: The data were collected on
a NoniusϪKappa CCD diffractometer with a rotating anode. The
structures were solved by direct methods using SHELXS-97 (2,
3)[47] or DIRDIF99 (1, 6Ϫ8)[48] and refined by least-squares pro-
cedures on F2 using SHELXL-97.[49] All non-hydrogen atoms were
refined with anisotropic displacement parameters. Hydrogen atoms
were constrained to idealized geometries and allowed to ride on
their carrier atoms with an isotropic displacement parameter re-
lated to the equivalent displacement parameter of their carrier
atoms. Compound 3 contained one phenyl ring on one of the phos-
phanes which is disordered over two positions. Compound 6 con-
tained four molecules of CDCl3 in the unit cell. Compound 7 con-
tained two acetone molecules which were disordered over two posi-
tions. Compound 8 contained disordered dichloromethane mol-
ecules. Their contribution was taken into account using the
PLATON/SQUEEZE procedure. Structure validation and molecu-
lar graphics preparation were performed with the PLATON pack-
age.[50] Crystal data are given in Tables 6 and 7. CCDC-213681
(1), -213682 (2), -213683 (3), -213684 (5), -213685 (6), -213686 (7),
and -213687 (8) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-
1
0.83 mmol). H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.46
(s, 6 H, m,p-CH2, c-C6), 2.18 (s, 4 H, o-CH2, c-C6), 3.55 (s, 6 H,
1
2
1
OCH3), 6.81 (dd, J ϭ 8.8, J ϭ 5.6 Hz, 2 H, H1), 7.32 (dd, J ϭ
8.8, 2J ϭ 2.4 Hz, 2 H, H2), 7.41 (dt, J ϭ 8.0, 2J ϭ 2.4 Hz, 8 H, o-
1
1
2
CH, PPh), 7.51 (dt, J ϭ 8.4, J ϭ 1.2 Hz, 4 H, p-CH, PPh), 7.65
(d, J ϭ 2.4 Hz, 2 H, H3), 7.69 (q, J ϭ 4.8 Hz, 8 H, m-CH, PPh).
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 22.7, 26.1, 37.0,
45.3, 55.2, 111.3 (d, JP,C ϭ 7.6 Hz), 128.0 (d, JP,C ϭ 12.3 Hz), 131.3
1
1
(d, JP,C ϭ 10.8 Hz), 132.8, 133.2, 133.9, 141.0, 158.6 (d, JP,C
ϭ
3.7 Hz). 31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ 27.7
(s). C44H42O4P2: calcd. C 75.85, H 6.08; found C 76.04, H 6.14.
trans,trans-[PdClCH3-2]2, Complex 6: Ligand 2 (40.2 mg, 60.5
µmol) and [PdClCH3(cod)] (13.9 mg, 52.4 µmol) were dissolved in
CDCl3 (0.5 mL) and the solution was stirred for 2 h before the
solution was analyzed by NMR spectroscopy. Single crystals were 1223-336033; E-mail: deposit@ccdc.cam.ac.uk].
Eur. J. Inorg. Chem. 2003, 4361Ϫ4369
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4367

J. I. van der Vlugt, M. M. P. Grutters, A. M. Mills, H. Kooijman, A. L. Spek, D. Vogt
FULL PAPER
Table 6. Selected crystallographic data for compounds 1Ϫ3 and 5
1
2
3
5
Formula
FW/Mr
C41H38O2P2
624.65
C44H42O2P2
664.72
C46H40O2P2
686.72
C44H42O4P2·H2O
714.73
Crystal size [mm]
Crystal system
Space group
0.12 ϫ 0.27 ϫ 0.42
monoclinic
C2/c (no. 15)
28.1693(3)
8.2166(1)
32.3533(4)
0.12 ϫ 0.15 ϫ 0.45
monoclinic
P21/c (no. 14)
17.4156(2)
7.8636(1)
28.3503(4)
0.21 ϫ 0.39 ϫ 0.48
triclinic
P1 (no. 2)
0.09 ϫ 0.21 ϫ 0.24
monoclinic
P21/c (no. 14)
12.2410(10)
11.9950(10)
27.398(3)
¯
˚
a [A]
11.1456(1)
12.0144(2)
15.0980(2)
89.1746(9)
70.6049(9)
80.4301(5)
1878.66(4)
0.153
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
115.7420(4)
113.2940(10)
114.279(11)
3
˚
V [A ]
6745.21(14)
0.164
3566.08(8)
0.159
3667.1(7)
0.165
µ (Mo-Kα) [mmϪ1
]
Z
8
4
2
4
dcalcd. [g cmϪ3
T [K]
]
1.230
150
1.238
150
1.214
150
1.295
150
Reflections collected
Unique reflections (Rint
26580
7617 (0.058)
5758
0.1025
0.71073
0.0411
1.02
28637
8121 (0.055)
5506
0.1063
0.71073
0.0452
1.03
27481
8452 (0.054)
6384
0.1159
0.71073
0.0431
4661
4661 (0.085)
3645
0.1921
0.71073
0.0785
1.13
[a]
)
Observed data [IϾ2.0σ(I)]
wR2 of F2 (all data)
˚
λ [A]
R1
S
1.03
Ϫ0.38, 0.35
3
˚
Min., max. residual electron density [e/A ]
Ϫ0.27, 0.32
Ϫ0.28, 0.28
Ϫ0.41, 0.53
[a]
2
2
2
2
2 2
2 2
Rint ϭ Σ[|Fo Ϫ Fo (mean)|]/Σ[Fo ]; wR(F2) ϭ {Σ[w(Fo Ϫ Fc ) ]/Σ[w(Fo ) ]}1/2; R(F) ϭ Σ(||Fo| Ϫ |Fc||)/Σ|Fo|.
Table 7. Selected crystallographic data for complexes 6Ϫ8
6
7
8
Formula
FW/Mr
C90H90Cl2O4P4Pd2·4 CDCl3
2124.68
C88H84O4P4Pt2·2 C3H6O
1977.57
C90H84O6P4Cl2Rh2·2 CH2Cl2
1832.13
Crystal size [mm]
Crystal system
Space group
0.06 ϫ 0.12 ϫ 0.18
triclinic
P1 (no.2)
0.21 ϫ 0.30 ϫ 0.36
monoclinic
P21/c (no.14)
14.4501(2)
19.5893(3)
16.5611(2)
0.21 ϫ 0.30 ϫ 0.36
monoclinic
P21/c (no.14)
14.3323(10)
19.9531(12)
¯
˚
a [A]
11.3951(2)
14.6487(2)
16.5314(2)
63.8137(6)
77.9245(6)
79.6576(8)
2409.47(6)
0.877
˚
b [A]
˚
c [A]
16.4423(19)
α [°]
β [°]
γ [°]
112.0310(6)
112.66(2)
3
˚
V (A )
4345.60(11)
3.465
4339.1(9)
0.682
µ (Mo-Kα) [mmϪ1
]
Z
1
2
2
dcalcd. [g cmϪ3
T [K]
]
1.462
150
1.511
150
1.272
150
Reflections collected
Unique reflections (Rint
37005
10960 (0.061)
8417
0.1176
0.71073
0.0479
42286
8532 (0.072)
6829
0.1106
0.71073
0.0587
1.36
82640
9954 (0.0505)
8179
0.070
0.71073
0.029
[a]
)
Observed data [IϾ2.0σ(I)]
wR2 of F2 (all data)
˚
λ [A]
R1
S
1.07
Ϫ0.73, 1.17
1.05
Ϫ0.49, 0.37
3
˚
Min., max. residual electron density [e/A ]
Ϫ0.91, 1.40
[a]
2
2
2
2
2 2
2 2
Rint ϭ Σ[|Fo Ϫ Fo (mean)|]/Σ[Fo ]; wR(F2) ϭ {Σ[w(Fo Ϫ Fc ) ]/Σ[w(Fo ) ]}1/2; R(F) ϭ Σ(||Fo| Ϫ |Fc||)/Σ|Fo|.
Acknowledgments
This work was financially supported by the National Research
School Combination for Catalysis (NRSCC) and in part (A.M.M.
and A.L.S.) by the Netherlands Foundation of Chemical Research
(SON) with financial aid from the Netherlands Organisation for
Scientific Research (CW-NWO). OMG is gratefully acknowledged
for a generous loan of metal precursors. We would like to thank
Dr. Rafael Sablong and Dr. Christian Müller (TU/e) for scientific
discussions.
4368
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 4361Ϫ4369

New Diphosphane Ligands Based on Bisphenol A Backbones
FULL PAPER
[24]
[25]
[26]
F. E. Wood, J. Hvoslef, H. Hope, A. L. Balch, Inorg. Chem.
1984, 23, 4309Ϫ4315.
B. E. Mann, C. Masters, B. L. Shaw, J. Chem. Soc. 1971,
1104Ϫ1106.
P. Suomalainen, S. Jääskeläinen, M. Haukka, R. H. Laitinen,
J. Pursiainen, T. A. Pakkanen, Eur. J. Inorg. Chem. 2000,
2607Ϫ2613.
[1]
C. A. Bessel, P. Aggarwal, A. C. Marschilok, K. J. Takeuchi,
Chem. Rev. 2001, 101, 1031Ϫ1066.
[2] [2a]
C. A. McAuliffe, Transition Metal Complexes of Phos-
[2b]
phorus, Arsenic and Antimony Ligands; New York, 1973.
C. A. McAuliffe, W. Levason, Phosphane, Arsane and Stibine
Complexes of the Transition Elements; Elsevier Science: New
York, 1978. [2c]D. M. A. Minahan, W. E. Hill, C. A. McAuliffe,
Coord. Chem. Rev. 1984, 55, 31.
W. Tang, X. Zhang, Chem. Rev. 2003, 103, 3029Ϫ3069.
W. Ahlers, R. Paciello, D. Vogt, J. I. van der Vlugt (to BASF
AG), US Patent Appl. 20020111517 [Chem. Abstract. 2002,
169060].
J. I. van der Vlugt, J. M. Bonet, A. M. Mills, A. L. Spek, D.
Vogt, Tetrahedron Lett. 2003, 44, 4389Ϫ4392.
[27]
M. J. Atherton, K. S. Coleman, J. Fawcett, J. H. Holloway, E.
G. Hope, A. Karacar, L. A. Peck, G. C. Saunders, J. Chem.
¸
Soc., Dalton Trans. 1995, 4029Ϫ4038.
L. Vaska, J. Peone Jr., J. Chem. Soc., Chem. Commun. 1971,
418Ϫ419.
K. G. Moloy, J. L. Petersen, J. Am. Chem. Soc. 1995, 117,
7696Ϫ7710.
F.-B. Xu, Q.-S. Li, X.-S. Zeng, X.-B. Leng, Z.-Z. Zhang, Or-
ganometallics 2002, 21, 4894Ϫ4896.
J. R. Dilworth, Y. Zheng, D. V. Griffiths, J. Chem. Soc., Dalton
Trans. 1999, 1877Ϫ1882.
C. M. Thomas, R. Mafua, B. Therrien, E. Rusanov, H. Stœckli-
Evans, G. Süss-Fink, Chem. Eur. J. 2002, 8, 3343Ϫ3352.
T. W. Graham, A. Llamazares, R. McDonald, M. Cowie, Or-
ganometallics 1999, 18, 3502Ϫ3510.
N. W. Alcock, J. M. Brown, J. C. Jeffery, J. Chem. Soc., Dalton
Trans. 1977, 888Ϫ893.
M. Cowie, S. K. Dwight, Inorg. Chem. 1980, 19, 2500Ϫ2507.
A. L. Balch, L. A. Fossett, M. M. Olmstead, D. E. Oram, P.
E. Reedy Jr., J. Am. Chem. Soc. 1985, 107, 5272Ϫ5274.
X. Liu, A. H. Eisenberg, C. L. Stern, C. A. Mirkin, Inorg.
Chem. 2001, 40, 2940Ϫ2941.
M. F. M. Al-Dulaymmi, D. L. Hughes, R. L. Richards, J. Or-
ganomet. Chem. 1992, 424, 79Ϫ86.
M. Cowie, S. K. Dwight, A. R. Sanger, Inorg. Chim. Acta 1978,
31, L407ϪL409.
D. R. Drew, J. R. Doyle, Inorg. Synth. 1990, 28, 346Ϫ349.
F. T. Ladipo, G. K. Anderson, Organometallics 1994, 13,
303Ϫ306.
[3]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[4]
[5]
[6]
Ullmann’s Encyclopedia of Industrial Chemistry, 6th electronic
edition, Wiley-VCH, Weinheim, 2002.
[7]
31P NMR spectroscopy in stereochemical analysis (Ed.: J. G Ver-
kade, L. D. Quin); VCH, Weinheim, 1987.
[8]
[8a] P. W. Baures, J. V. Silverton, Acta Crystallogr., Sect. C 1990,
46, 715Ϫ717. [8b] P. W. Baures, Acta Crystallogr., Sect. C 1991,
[8c]
47, 2715Ϫ2716.
C. Lariucci, R. Helena de Almeida Santos,
J. R. Lechat, Acta Crystallogr., Sect. C 1986, 42, 1825Ϫ1828.
M. R. Churchill, R. F. See, S. L. Randall, J. D. Atwood, Acta
Crystallogr., Sect. C 1993, 49, 345Ϫ347.
S. Gladiali, S. Pulacchini, D. Fabbri, M. Manassero, M. San-
soni, Tetrahedron: Asymmetry 1998, 9, 391Ϫ395.
[9]
[35]
[36]
[10]
[37]
[38]
[39]
[11] [11a]
W. J. Marshall, V. V. Grushin, Organometallics 2003, 22,
[11b]
555Ϫ562.
S. Priya, M. S. Balakrishna, J. T. Mague, S. M.
[11c]
Mobin, Inorg. Chem. 2003, 42, 1272Ϫ1281.
T.-W. Teo, S.
Selvaratnam, J. J. Vittal, P.-H. Leung, Inorg. Chim. Acta 2003,
352, 213Ϫ219.
[40]
[41]
[12]
[13]
[14]
T. B. Rauchfuss, F. T. Patino, D. M. Roundhill, Inorg. Chem.
1975, 14, 652Ϫ656.
W. Marty, P. N. Kapoor, H. B. Bürgi, E. Fischer, Helv. Chim.
[42]
H. C. Clark, L. E. Manzer, J. Organomet. Chem. 1973, 59,
411Ϫ428.
Acta 1987, 70, 158Ϫ170.
M. A. Zuideveld, B. H. G. Swennenhuis, M. D. K. Boele, Y.
Guari, G. P. F. van Strijdonck, J. N. H. Reek, P. C. J. Kamer,
K. Goubitz, J. Fraanje, M. Lutz, A. L. Spek, P. W. N. M. van
Leeuwen, J. Chem. Soc., Dalton Trans. 2002, 2308Ϫ2317.
K. Takenaka, Y. Obora, L. H. Jiang, Y. Tsuji, Organometallics
2002, 21, 1158Ϫ1166.
A. Mentes, R. D. W. Kemmitt, J. Fawcett, D. R. Russeli, Poly-
hedron 1999, 18, 1141Ϫ1145.
S. J. Young, B. Kellenberger, J. H. Reibenspies, S. E. Himmel,
M. Manning, O. P. Anderson, J. K. Stille, J. Am. Chem. Soc.
1988, 110, 5744Ϫ5753.
[43] [43a]
N. Yonezawa, T. Hino, Y. Tokita, K. Matsuda, T. Ikeda,
[43b]
Tetrahedron 1997, 53, 14287Ϫ14296.
S. H. Dai, C. Y. Lin,
D. V. Rao, F. A. Stuber, P. S. Carleton, H. Ulrich, J. Org. Chem.
1985, 50, 1722Ϫ1725.
B. Gerharz, G. Meier, E. W. Fischer, J. Chem. Phys. 1990, 92,
7110Ϫ7122.
[15]
[16]
[17]
[44]
[45]
I. E. Marko, J. M. Southern, M. L. Kantam, Synlett 1991, 4,
[45a]
235Ϫ237.
I. E. Marko, M. L. Kantam, Tetrahedron Lett.
1991, 32, 2255Ϫ2258.
[46] [46a]
A. Studer, M. Bossart, T. Vasella, Org. Lett. 2000, 2,
[46b]
985Ϫ988.
C. A. van Walree, X. Y. Lauteslager, A. M. A.
[18]
[19]
A. Pryde, B. L. Shaw, B. Weeks, J. Chem. Soc., Dalton Trans.
1976, 322Ϫ327.
C. E. Housecroft, B. A. M. Shaykh, A. L. Rheingold, B. S.
Haggerty, Inorg. Chem. 1991, 30, 125Ϫ130.
van Wageningen, J. W. Zwikker, L. W. Jenneskens, J. Or-
ganomet. Chem. 1995, 496, 117Ϫ125.
[47]
[48]
G. M. Sheldrick, SHELXS-97. University of Göttingen, Ger-
many, 1997.
[20] [20a]
J. A. Davies, S. Dutremez, A. A. Pinkerton, M. Vilmer,
P. T. Beurskens, G. Beurskens, R. de Gelder, S. Garcia-Granda,
¸
Organometallics 1991, 10, 2956Ϫ2958. [20b] C. B. Pamplin, S. J.
Rettig, B. O. Patrick, B. R. James, Inorg. Chem. 2003, 42,
4117Ϫ4126.
R. O. Gould, R. Israel, J. M. M. Smits, The DIRDIF99 Pro-
gram System, University of Nijmegen, The Netherlands, 1999.
G. M. Sheldrick, SHELXL-97. University of Göttingen, Ger-
many, 1997.
A. L. Spek, PLATON, A Multipurpose Crystallographic Tool,
Utrecht University, The Netherlands, 2002.
Received June 30, 2003
[49]
[50]
[21]
[22]
[23]
C. J. Cobley, P. G. Pringle, Inorg. Chim. Acta 1997, 265,
107Ϫ115.
N. W. Alcock, L. Judd, P. G. Pringle, Inorg. Chim. Acta 1986,
113, L13ϪL15.
F. C. March, R. Mason, K. M. Thomas, B. L. Shaw, J. Chem.
Soc., Chem. Commun. 1975, 584Ϫ585.
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