Synthesis and structure of Pt(II) phosphonato-phosphine complexes and of a P,O-stabilized metal-metal-bonded Pt2Ag2 complex

Article abstract of DOI:10.1021/ic0485559

As part of our interest in the design and reactivity of P,O ligands, and because the insertion chemistry of small molecules into a metal alkyl bond is very dependent on the ancillary ligands, the behavior of Pt-methyl complexes containing the β-phosphonat

Full text of DOI:10.1021/ic0485559

Inorg. Chem. 2005, 44, 1391−1403
Synthesis and Structure of Pt(II) Phosphonato-Phosphine Complexes
and of a P,O-Stabilized Metal Metal-Bonded Pt2Ag2 Complex
−
Nicola Oberbeckmann-Winter,† Xavier Morise,† Pierre Braunstein,*,† and Richard Welter‡
Laboratoire de Chimie de Coordination and Laboratoire DECMET, UMR 7513 CNRS,
UniVersite´ Louis Pasteur, 4 rue Blaise Pascal, F-67070 Strasbourg Ce´dex, France
Received October 15, 2004
As part of our interest in the design and reactivity of P,O ligands, and because the insertion chemistry of small
molecules into a metal alkyl bond is very dependent on the ancillary ligands, the behavior of Pt methyl complexes
containing the -phosphonato-phosphine ligand rac-Ph2PCH(Ph)P(O)(OEt)2 (abbreviated PPO in the following) toward
CO insertion has been explored. New, mononuclear Pt(II) complexes containing one or two PPO ligands, [PtClMe-
−
â
(
(
κ
κ
2-PPO)] (1), [Pt
1-PPO)2] (5), [PtMe(
1-PPO)]BF4 (7
‚
{
C(O)Me
2-PPO)(
BF4) have been prepared and characterized. Hemilability of the ligands is observed in the
}
Cl(
κ
2-PPO)] (2), [PtMe(CO)(
κ
2-PPO)]OTf (3
2-PPO)(
‚
κ
OTf), [PtMe(OTf)(
κ
2-PPO)] (4), trans-[PtClMe-
C(O)Me
κ
κ
1-PPO)]BF4 (6
‚
BF4), [PtMe(
κ
1-PPO)]OTf (6
‚
OTf), and [Pt
{
}( -
κ2
PPO)(
κ
cations 6 and 7 in which the terminally bound and chelating PPO ligands exchange their role on the NMR time-
scale. The acetyl complexes 2 and 7 are stable in solution, but the former deinserts CO upon chloride abstraction.
We also demonstrate the ability of PPO to behave as an assembling ligand and to stabilize a heterometallic Pt
metal complex, [PtMe( Ag(OTf)(Pt Ag)]OTf (8 OTf), which was obtained by reaction
2-PPO){µ-( 1-P; 1-O)PPO)
of 5 with AgOTf to generate more reactive, cationic complexes. Whereas the first equivalent of AgOTf abstracted
the chloride ligand, the second equivalent added to the cationic complex with formation of a Pt Ag bond (2.819(1)
Å). The complexes 1, 2, 4, 5 CH2Cl2, and (8 OTf)2 have been structurally characterized by single-crystal X-ray
diffraction. The latter has a dimeric nature in the solid state, with two silver-bound triflates acting as bridging
ligands between two Pt Ag moieties. In addition to the Ag
Pt bond, the Ag+ cation is stabilized by a dative O
Ag interaction involving one of the PPO ligands.
−Ag
κ
η
η
}
−
‚
−
‚
‚
−
−
f
Introduction
competing donors are present and the preparation of metal
complexes displaying catalytic properties or hemilability of
their coordinated ligands. The latter aspect has direct
relevance to delineating the conditions for the occurrence
of intramolecular dynamic behavior of functional ligands and
its implications in molecular activation and homogeneous
catalysis.1
We have noted recently that phosphine ligands containing
a phosphoryl function, that is, phosphinate, phosphonate, or
phosphate, have received relatively little attention2 in contrast
to the phosphine oxide ligands, although it has been
structurally proven that their PdO group can coordinate to
a metal center via the oxygen atom,2,3 including in the case
of the softer palladium4 or platinum5 ions. Such ligands could
be used as potential P,O chelates, likely to display hemilabile
behavior under suitable conditions, or as assembling ligands
in the formation of di- or polymetallic metal complexes. As
The increasing interest in organometallic and coordination
chemistry for functional phosphine ligands whose donor
atoms significantly differ in their hard-soft properties has
been discussed in recent review articles.1 In particular, this
has stimulated the synthesis of various P,O ligands in which
a phosphine moiety is associated with carboxylate, ketone,
alcohol, ether, ester, sulfoxide, or phosphine oxide functions.
Main motivations include a better understanding of the
requirements for selective metal-ligand interactions when
* Author to whom correspondence should be addressed. E-mail:
braunst@chimie.u-strasbg.fr.
† Laboratoire de Chimie de Coordination.
‡ Laboratoire DECMET.
(1) (a) Bader, A.; Lindner, E. Coord. Chem. ReV. 1991, 108, 27. (b)
Lindner, E.; Pautz, S.; Haustein, M. Coord. Chem. ReV. 1996, 15,
145. (c) Slone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog. Inorg.
Chem. 1999, 48, 233. (d) Braunstein, P.; Naud, F. Angew. Chem., Int.
Ed. 2001, 40, 680. (e) Braunstein, P. J. Organomet. Chem. 2004, 689,
3953 and references therein.
(2) Morise, X.; Braunstein, P.; Welter, R. Inorg. Chem. 2003, 42, 7752.
Inorganic Chemistry, Vol. 44, No. 5, 2005 1391
10.1021/ic0485559 CCC: $30.25
Published on Web 02/09/2005
© 2005 American Chemical Society

Oberbeckmann-Winter et al.
Scheme 1. Possible Reaction Products between [PtClMe(cod)] and a
Bifunctional P,O Ligand
part of our interest in the design and reactivity of P,O
ligands,1d we have recently reported the synthesis of the first
enolphosphato-phosphine ligands, Ph2PCHdCPh[OP(O)-
(OR)2] (R ) Et, Ph),2 and of the new â-phosphonato-
phosphine ligand rac-Ph2PCH(Ph)P(O)(OEt)2,6 which asso-
ciate P(III) and P(V) donor centers. They form with Pd(II)
complexes seven- or five-membered rings, respectively, and
some of them display hemilabile behavior.
In view of the difficulties often encountered in isolating
Pd(II) reaction intermediates because of their high reactivity
or instability, Pt(II) complexes are often taken as valuable
models because their isolation and full characterization is
easier. Furthermore, cationic Pt-methyl complexes of an
enantiomerically pure chelating P,N ligand have been
recently used in asymmetric catalysis.7 Because the insertion
chemistry of small molecules into a metal-alkyl bond is very
dependent on the ancillary ligands, we decided to explore
the behavior of Pt-methyl complexes containing the â-phos-
phonato-phosphine ligand rac-Ph2PCH(Ph)P(O)(OEt)26 (ab-
breviated PPO in the following) toward CO insertion. We
also describe the ability of PPO to behave as an assembling
ligand and to stabilize a heterometallic Pt-Ag metal complex
obtained in the course of studies aiming at generating more
reactive, cationic complexes. The new compounds 1, 2, 4,
5‚CH2Cl2, and (8‚OTf)2 have been structurally characterized
by X-ray diffraction.
again B as the main product, but the cis-isomer C could also
be detected. In both cases, the products have been identified
by 1H and 31P{1H} NMR spectroscopy.10 For compounds of
type B, the Pt-bound methyl group appears as a triplet in
the 1H NMR spectrum due to coupling with two equivalent
PPh2 nuclei, whereas a doublet of doublets was observed
for the methyl group of C because of the presence of two
nonequivalent PPh2 functions. As is often the case for
complexes with two mutually trans phosphorus nuclei, the
large 2JP-P coupling leads to the appearance of virtual triplets
1
in the H NMR spectra for the protons R to phosphorus.11
This was also observed for the NH proton in trans-[PtClMe-
{κ1-Ph2PNHC(O)Me}2].10
To see whether the formation of A could become more
selective and that of species B and C avoided, we decided
to use the recently synthesized PPO ligand and reacted it
with [PtClMe(cod)]. This afforded [PtClMe(κ2-PPO)] (1) as
a main product with small amounts of the B-type complex
5 (ca. 9:1 ratio), and formation of C was not observed (eq
1).
Results and Discussion
Synthesis of Pt(II) Complexes Containing One PPO
Ligand. Earlier studies on the coordination properties of
other P,O ligands led us to perform the reaction of the
acetamido-derived phosphine ligand Ph2PNHC(O)Me8 with
1 equiv of [PtClMe(cod)] (cod ) 1,5-cyclooctadiene)
(Scheme 1). This afforded exclusively product B after stirring
for 2 h in CH2Cl2. The remaining half equivalent of the Pt
precursor did not react with B to give the desired product A
when stirring was continued overnight. An analogous reac-
tion with the ketophosphine ligand Ph2PCH2C(O)Ph9 yielded
(3) See, for example: (a) DeBolster, M. W. G.; Goeneveld, W. L. In
Topics in Phosphorus Chemistry; Griffith, E. J., Grayson, M., Eds.;
Wiley: New York, 1976; Vol. 8, p 273 and references therein. (b)
Gahagan, M.; Mackie, R. K.; Cole-Hamilton, D. J.; Cupertino, D. C.;
Harman, M.; Hursthouse, M. B. J. Chem. Soc., Dalton Trans. 1990,
2195. (c) Weis, K.; Rombach, M.; Vahrenkamp, H. Inorg. Chem. 1993,
32, 2470. (d) Kingsley, S.; Chandrasekhar, V.; Incarvito, C. D.; Lam,
M. K.; Rheingold, A. L. Inorg. Chem. 2001, 40, 5890.
(4) (a) Jessup, J. S.; Duesler, E. N.; Paine, R. T. Inorg. Chim. Acta 1983,
73, 261. (b) Kla¨ui, W.; Glaum, M.; Wagner, T.; Bennett, M. A. J.
Organomet. Chem. 1994, 472, 355. (c) Domhover, B.; Hamers, H.;
Kla¨ui, W.; Pfeffer, M. J. Organomet. Chem. 1996, 522, 197. (d) Kla¨ui,
W.; Glaum, M.; Hahn, E.; Lugger, T. Eur. J. Inorg. Chem. 2000, 21.
(5) (a) Nettle, A.; Valderrama, M.; Contreras, R.; Scotti, M.; Peters, K.;
von Schnering, H. G.; Werner, H. Polyhedron 1988, 7, 2095. (b)
Marsh, R. E.; Schaefer, W. P.; Lyon, D. K.; Labinger, J. A.; Bercaw,
J. E. Acta Crystallogr., Sect. C 1992, 48, 1603. (c) Contreras, R.;
Valderrama, M.; Nettle, A.; Boys, D. J. Organomet. Chem. 1997, 527,
125.
These results show the influence of the phosphine and
phosphonato donor functions on the reactivity of their Pt(II)
complexes when compared to the P,O donors of Ph2PNHC-
(O)Me or Ph2PCH2C(O)Ph. There is no obvious angular
parameter that could explain the greater propensity for ligand
(10) Selected NMR data for trans-[PtClMe{κ1-Ph2PNHC(O)Me}2], 1H
3
2
NMR (300.13 MHz, CDCl3) δ: -0.19 (t, JP-H ) 7.4 Hz, JPt-P
)
80 Hz, PtCH3), 8.81 (virtual t, | JP-H + 4JP-H| ) 20.2 Hz, NH). 31P-
2
{1H} NMR (121.49 MHz, CDCl3) δ: 48.6 (s, JPt-P ) 3210 Hz).
1
Selected NMR data for trans-[PtClMe{κ1-Ph2PCH2C(O)Ph}2], 1H
3
2
NMR (300.13 MHz, CDCl3) δ: -0.13 (t, JP-H ) 6.8 Hz, JPt-P
)
81 Hz, PtCH3). 31P{1H} NMR (121.49 MHz, CDCl3) δ: 22.4 (s, 1JPt-P
) 3173 Hz). Selected NMR data for cis-[PtClMe{κ1-Ph2PCH2C(O)-
Ph}2], 1H NMR (300.13 MHz, CDCl3) δ: 0.64 (dd, 3JP-H ) 7.5 Hz,
3JP-H ) 4.8 Hz, 2JPt-P ) 56 Hz, PtCH3). 31P{1H} NMR (121.49 MHz,
CDCl3) δ: 11.7 (d, 2JP-P ) 13 Hz, 1JPt-P ) 4582 Hz, P trans to Cl),
(6) Morise, X.; Braunstein, P.; Welter, R. C. R. Chim. 2003, 6, 91.
(7) Blacker, A. J.; Clarke, M. L.; Loft, M. S.; Mahon, M. F.; Williams,
J. M. J. Organometallics 1999, 18, 2867.
(8) Braunstein, P.; Frison, C.; Morise, X.; Adams, R. D. J. Chem. Soc.,
Dalton Trans. 2000, 2205.
(9) Bouaoud, S.-E.; Braunstein, P.; Grandjean, D.; Matt, D.; Nobel, D.
Inorg. Chem. 1986, 25, 3765.
2
1
18.5 (d, JP-P ) 13 Hz, JPt-P ) 1752 Hz, P trans to Me).
(11) (a) Verstuyft, A. W.; Nelson, J. H.; Redfield, D. A.; Cary, L. W. Inorg.
Chem. 1976, 15, 1128. (b) Verstuyft, A. W.; Redfield, D. A.; Cary,
L. W.; Nelson, J. H. Inorg. Chem. 1977, 16, 2776.
1392 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
Figure 1. View of the molecular structure of 1 with thermal ellipsoids
drawn at the 50% probability level. The hydrogen atoms except H1 and
the non-ipso aryl carbons of the PPh2 group have been omitted for clarity.
Figure 2. View of the molecular structure of 2 with thermal ellipsoids
drawn at the 50% probability level. The hydrogen atoms except H1 and
the non-ipso aryl carbons of the PPh2 group have been omitted for clarity.
Scheme 2. Synthesis of Complexes 1-4
chelation in the case of the PPO ligand (such as the PCP or
CPO angles as compared to the related angles in the other
P,O ligands) so that electronic effects dominate with a greater
coordinating ability of the PdO function as compared to the
CdO group of the amide or ketone function of the other
P,O ligands. In the course of attempts to optimize the reaction
conditions, it was found that slow addition of PPO did not
influence the product ratio. After addition of a CDCl3 solution
of PPO to 1 equiv of solid [PtClMe(cod)], monitoring of
the reaction by 1H and 31P{1H} NMR spectroscopy showed
after 10 min the formation of a 1:2 mixture of the kinetically
favored 5 and the thermodynamically favored 1. The
proportion of 1 clearly increases with time. We could show
in a separate experiment that transfer of the monodentate
PPO ligand from the bis-substituted complex 5 to [PtClMe-
(cod)] is possible and yields the desired product 1. Indeed,
31P{1H} NMR monitoring of the evolution of an equimolar
mixture of 5 and [PtClMe(cod)] in CDCl3 showed the
progressive formation of the thermodynamic product 1 within
3-4 days. Complex 1 can therefore be obtained from the
direct reaction of [PtClMe(cod)] with 1 equiv of PPO or
indirectly, from 5 and [PtClMe(cod)]. The X-ray structure
of 1 is discussed below (Figure 1).
Figure 3. View of the molecular structure of 4 with thermal ellipsoids
drawn at the 50% probability level. The hydrogen atoms except H1 and
the non-ipso aryl carbons of the PPh2 group have been omitted for clarity.
compared to the shifts observed in related neutral or cationic
Pd(II) complexes, which amount to 10-15 ppm.12 However,
the Pt-P coupling constant and the 195Pt{1H} NMR chemical
shifts are very different in the alkyl and acyl complexes:
the Pt-P coupling constant increases by 425 Hz, and the
195Pt{1H} NMR signal undergoes a downfield shift of ca.
670 ppm when going from 1 to 2.
Reaction between 2 and 1 equiv of AgOTf (OTf ) SO3-
CF3) led to halide abstraction, but the direct metathesis
product with a coordinated triflate could not be isolated.
Instead, CO deinsertion occurred and [PtMe(CO)(κ2-PPO)]-
OTf (3‚OTf) was isolated in good yield. The latter complex
could also be synthesized by first substituting the chloride
for triflate in 1, to obtain 4, which was fully characterized
including by X-ray diffraction (Figure 3 and see below), and
then exposing its CH2Cl2 solution to a CO atmosphere for 2
h. Because the CO ligand in 3 prefers to avoid being trans
to P, the methyl group is now trans to P, in contrast to the
situation in 1, and these observations are in agreement with
the thermodynamic preference for high trans-influence
ligands to avoid being in mutual trans position.13 In contrast
CO insertion into the Pt-Me bond of 1 afforded the acetyl
complex 2 (Scheme 2), which was fully characterized,
including by X-ray diffraction (Figure 2 and see below). The
31P{1H} NMR chemical shift is here a poorer indicator of
the transformation alkylfacyl (∆δP(PPh2) ) 2 ppm) when
(12) (a) Braunstein, P.; Frison, C.; Morise, X. Angew. Chem., Int. Ed. 2000,
39, 2867. (b) Braunstein, P.; Morise, X.; Hamada, A., unpublished
results.
Inorganic Chemistry, Vol. 44, No. 5, 2005 1393

Oberbeckmann-Winter et al.
Table 1. Comparison of Selected 31P{1H} NMR Data for the PPh2
Table 2. Selected Bond Distances (Å) and Angles (deg) for 1, 2, and 4
Group
1
2
4
δ/ppm
48.6
1JPt-P/Hz
Pt-C24
2.0316(4)
2.389(2)
2.145(2)
2.231(5)
1.973(8)
2.344(2)
2.212(2)
2.263(5)
2.025(5)
trans-[PtClMe{κ1-Ph2PNHC(O)Me}2]
trans-[PtClMe{κ1-Ph2PCH2C(O)Ph}2]
cis-[PtClMe{κ1-Ph2PCH2C(O)Ph}2]
P trans to Cl
3210
3173
Pt-Cl
22.4
Pt-P1
2.156(1)
2.227(3)
2.127(3)
1.496(3)
Pt-O1
11.7
4582
1752
4661
5086
1294
5360
4828
4335
3250/3242
4012
3336
1556
Pt-O4
P trans to Me
18.5
P2-O1
1.491(5)
1.482(5)
1.192(9)
92.7(2)
177.1(3)
88.2(1)
[PtClMe(κ2-PPO)] (1)
14.2a
12.2b
34.0b
9.9a
C24-O4
[Pt{C(O)Me}Cl(κ2-PPO)] (2)
trans-[PtMe(CO)(κ2-PPO)]+ (3)
[PtMe(OTf)(κ2-PPO)] (4)
[PtMe(NCMe)(κ2-PPO)]+
[PtMe(C2H4)(κ2-PPO)]+
C24-Pt-P1
C24-Pt-O1
P1-Pt-O1
C24-Pt-Cl
C24-Pt-O4
O1-Pt-Cl
O1-Pt-O4
Pt-C24-O4
93.64(6)
176.4 (1)
89.8(1)
93.4(2)
176.6(2)
89.96(9)
12.9a
19.4a
32.8/32.9
18.4b
25.3a,c
31.2a,c
88.92(6)
89.5(2)
90.3(2)
86.4(1)
trans-[PtClMe(κ1-PPO)2] (5)d
[PtMe(tht)(κ2-PPO)]+ (9)
cis-[PtMe(CO)(κ2-dppmS)]+
trans-[PtMe(CO)(κ2-dppmS)]+
87.7(1)
89.8(1)
122.0(7)
a In CD2Cl2. b In CDCl3. c From ref 14. d Presence of diastereomers.
planar coordination geometry. There are only small variations
in the Pt-CMe distance, which is 2.0316(4) Å for 1 and
2.025(5) Å for 4, but in the acetyl complex 2 the Pt-C(O)Me
bond is at 1.973(8) Å slightly shorter. The Pt-C(24)-O(4)
plane of the acetyl ligand is oriented almost perpendicular
to the metal coordination plane (dihedral angle between the
“best planes” of 81(1)°), which is usual for Pt(II)- and Pd-
(II)-acyl complexes.15 The Pt-C(24)-O(4) angle of 122.0-
(7)° is typical for a η1-coordination mode, in contrast to the
smaller angle for a η2-coordination.16 The two Pt-Cl
distances for 1 and 4 are also in the expected range (2.389-
(2) Å for 1 and 2.344(2) Å for 4). A significant difference
was found for the angle between the Pt center and the
aromatic rings of the phosphine moiety. In the solid-state
structure of 2, one of the two phenyl groups is oriented nearly
parallel to the Pt-PPPh2 axis (torsion angle Pt-P1-C14-
C15: -10.7(7)°) so that the Pt-H15 distance is 2.99(1) Å.
This is the shortest Pt-H distance found for these three
complexes, and a weak interaction cannot be excluded,
although packing effects might also be the reason for this
orientation. No further significant intra- or intermolecular
interactions were found.
Because cationic Pt(II)-acetyl complexes readily deinsert
CO when no strong donor ligand is available to block a
potentially vacant coordination site in cis position, we were
interested in obtaining a cationic methyl Pt(II) system,
anticipated to be more reactive than a neutral complex such
as 1 toward CO insertion, and in which the ancillary ligand
could provide an intramolecular donor to block the tempo-
rarily vacant coordination site after halide abstraction. For
this reason, we investigated the synthesis of complexes
containing two PPO ligands.
to the present study where a carbonyl complex with the cis-
Me-Pt-PPh2 arrangement could not be detected, the kinetic
product with a cis-Me-Pt-PPh2 arrangement was observed
in the related complex [PtMe(CO)(dppmS)]+ which contains
a bis(phosphanyl)monosulfide ligand, and its isomerization
to the trans structure proceeded only slowly.14 This behavior
reflects the difference in the nature of the OfPt and SfPt
dative bonds between these complexes. A good indicator for
1
the cis/trans geometry is the value of the JPt-P coupling
constant, which was found to be about 1300 Hz for complex
3‚OTf (Table 1). This small value is typical for a PPh2 moiety
trans to an alkyl group. In the 13C{1H} NMR spectrum of
3‚OTf, the 2JP-C value for the methyl group bonded to Pt is
74 Hz, whereas it was around 7 Hz for compounds 1 and 4.
The triflate group in 4 can be displaced by MeCN or C2H4
to give the corresponding cationic complexes [PtMe(L)(κ2-
PPO)]+ (L ) MeCN, C2H4) in which the methyl group
remains trans to oxygen (1H and 31P{1H} NMR monitoring);
no isomerization was observed, which is consistent with these
ligands having a weaker trans-influence than a methyl or a
CO group. That both MeCN and C2H4 are better donors than
triflate is consistent with the decrease in the 1JPt-P coupling
constant for the trans phosphine moiety (see Table 1 and
Experimental Section).
Reaction of 2 with AgOTf in CH2Cl2 under ethylene
atmosphere also led to the formation of 3, so that deinsertion/
coordination of CO appears more favorable than coordination
of C2H4 to the vacant site created by chloride abstraction.
Complex 3‚OTf was found to decompose when kept in a
CDCl3 solution at room temperature. This is likely to be due
to progressive loss of CO, because after approximately 1
week traces of 4 could be detected in the 31P{1H} NMR
spectrum, but no 1 was found as a reaction product between
3 and the chlorinated solvent.
Synthesis of Pt(II) Complexes Containing Two PPO
Ligands. The precursor to a series of Pt(II) complexes
containing two PPO ligands, [PtClMe(κ1-PPO)2] (5) (Scheme
3), was obtained either by addition of 2 equiv of PPO to
[PtClMe(cod)] or of 1 equiv of PPO to 1. Because of the
The molecular structures of compounds 1, 2, and 4 have
been determined by X-ray diffraction (Figures 1-3, Table
2). In all three complexes, the platinum has a typical square-
(15) See, for example: (a) Ru¨lke, R. E.; Delis, J. G. P.; Groot, A. M.;
Elsevier, C. J.; van Leeuwen, P. W. N. M.; Vrieze, K.; Goubitz, K.;
Schenk, H. J. Organomet. Chem. 1996, 508, 109. (b) Gerisch, M.;
Heinemann, F. W.; Bruhn, C.; Scholz, J.; Steinborn, D. Organome-
tallics 1999, 18, 564.
(13) (a) Pearson, R. G. Inorg. Chem. 1973, 12, 712. (b) Davies, J. A.;
Hartley, F. R. Chem. ReV. 1981, 81, 79. (c) Vicente, J.; Arcas, A.;
Bautista, D.; Jones, P. G. Organometallics 1997, 16, 2127.
(14) Mastrorilli, P.; Nobile, C. F.; Suranna, G. P.; Fanizzi, F. P.; Ciccarella,
G.; Englert, U.; Li, Q. Eur. J. Inorg. Chem. 2004, 1234.
(16) For a review on η2-acyl coordination, see: Durfee, L. D.; Rothwell,
I. P. Chem. ReV. 1988, 88, 1059.
1394 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
Scheme 3. Synthesis of Complexes 5-7
presence of a stereogenic center in the PPO ligand, a mixture
of two pairs of diastereomers was obtained that we did not
attempt to separate. Consistently, the 31P{1H} NMR spectrum
contained two very closely spaced singlets for the mutually
trans PPh2 groups, and two singlets for the PdO groups. In
contrast to the 31P{1H} NMR spectra for compounds 1-4,
no JP(O)-P coupling was detected in the case where PPO acts
as a monodentate ligand. The trans ligand arrangement in 5
was again established by the appearance of virtual triplets
in both the 1H and the 13C{1H} NMR spectra for the signals
of the CHPh group R to phosphorus.11
The X-ray structure determination of 5 established the
bonding parameters in the RS/SR pair (see Figure 4, Table
3). The two phosphorus atoms are mutually trans with an
angle P1-Pt-P3 of 177.42(2)°. The Pt-CMe distance of
2.061(3) Å is slightly longer than that in complexes 1, 2,
and 4. Similarly, the Pt-Cl bond of 2.4288(9) Å is slightly
longer than that in complexes 1 and 4.
Chloride abstraction from 5 using AgBF4 or AgOTf
afforded the cationic complex [PtMe(κ2-PPO)(κ1-PPO)]+ 6
in which the two phosphine moieties are still mutually trans
and one of the PPO ligand has become a chelate. Variable-
temperature 31P{1H} NMR spectroscopy established that the
phosphonato groups of 6‚OTf are exchanging at room
temperature, which leads to only one broad signal in 31P-
{1H} NMR that becomes a triplet at higher temperature (see
the variable-temperature 31P{1H} NMR spectrum in Figure
S-1 and the P,P-COSY spectrum of 6 in Figure S-2 of the
Supporting Information). Consistently, for the mixture of
diastereomers, each of the two PPh2 resonances appears as
a triplet in the dynamic regime due to coupling with two
PdO functions, which appear equivalent on the NMR time-
scale. Related observations have been made, for example,
in the case of complexes with a dangling η1-dppm ligand
that undergoes an “end over end” P,P exchange at room
temperature.17 The broadening of the PdO resonance at room
temperature is also due to the presence of a mixture of
diastereomers with very similar chemical shifts. Therefore,
the 31P{1H} NMR spectrum at low temperature shows not
only the signals for coordinated and noncoordinated PdO
moieties, but also for the two pairs of diastereomers.
Figure 4. View of the molecular structure of 5 in 5‚CH2Cl2 with thermal
ellipsoids drawn at the 50% probability level. The hydrogen atoms except
H1 and H25, the non-ipso aryl carbons of the PPh2 group and the solvent
molecule have been omitted for clarity.
Table 3. Selected Bond Distances (Å) and Angles (deg) for 5‚CH2Cl2
and (8‚OTf)2
5
(8‚OTf)2
(8‚OTf)2
Pt-C24
Pt-Cl
2.061(3)
2.4288(9)
2.3009(9)
2.3092(9)
1.456(3)
1.463(2)
88.35(8)
89.86(8)
177.42(2)
2.033(5) Pt-O1
Pt-Ag
2.284(1) Ag-O4
2.317(1) Ag-O7
1.493(4) Ag-O8a′
1.479(4) C24-Pt-O1
2.188(3)
2.819(1)
2.234(5)
2.261(6)
2.471(5)
175.6(2)
87.7(1)
92.8(1)
89.72(3)
81.5(1)
Pt-P1
Pt-P3
P2-O1
P4-O4
C24-Pt-P1
C24-Pt-P3
P1-Pt-P3
89.1(2)
90.2(2)
175.84(4)
P1-Pt-O1
P3-Pt-O1
P1-Pt-Ag
O1-Pt-Ag
P3-Pt-Ag
C24-Pt-Ag
P4-O4-Ag
C24-Pt-Cl1 174.19(9)
P1-Pt-Cl
P3-Pt-Cl
92.73(4)
88.86(4)
94.44(3)
101.5(2)
135.6(3)
O7-Ag-O8a′ 103.6(2)
O4-Ag-O7
136.5(2)
94.6(2)
O4-Ag-O8a′
Carbonylation of 6‚BF4 in CH2Cl2 at room temperature
under CO atmosphere afforded a diastereomeric mixture of
the acetyl complex 7‚BF4. The chemical shifts of the
phosphine moieties are more separated than in the case of
6‚BF4, and the broad PdO resonance is again consistent with
a dynamic exchange of the chelating and monodentate PPO
ligands. In general, acetyl ligands are less common in cationic
than in neutral Pt-complexes, and only eight crystal structures
of cationic acetyl Pt-complexes were found in the CSD (CSD
version 5.25). Interestingly, complex 7 does not readily
decarbonylate because of the presence of two strong phos-
phorus donors in cis position to the acetyl ligand. Related
acetyl-Pd(II) complexes with two mutual trans phosphines
have been investigated in alkoxycarbonylation reactions, with
the alcoholysis of the Pd-acetyl bond being a key step of
the reaction.18 We were therefore interested in the behavior
of 7‚BF4 when its CH2Cl2 solution is exposed to an
atmosphere of ethylene for 12 h, but no insertion of C2H4
was observed. A possible explanation for the inertness of
compound 7‚BF4 against olefin insertion is that the required
(18) (a) van Leeuwen, P. W. N. M.; Zuideveld, M. A.; Swennenhuis, B.
H. G.; Freixa, Z.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.; Lutz, M.;
Spek, A. L. J. Am. Chem. Soc. 2003, 125, 5523. (b) Liu, J.; Heaton,
B. T.; Iggo, J. A.; Whyman, R. Chem. Commun. 2004, 1326.
(17) Braunstein, P.; de Me´ric de Bellefon, C.; Oswald, B.; Ries, M.;
Lanfranchi, M.; Tiripicchio, A. Inorg. Chem. 1993, 32, 1638 and
references therein.
Inorganic Chemistry, Vol. 44, No. 5, 2005 1395

Oberbeckmann-Winter et al.
Figure 5. View of the molecular structure of (8‚OTf)2 with thermal ellipsoids drawn at the 30% probability level except for F1, F2, and F3 which for
clarity have been represented with only very small ellipsoids. The hydrogen atoms except H1 and H25, the non-ipso aryl carbons of the PPh2 group and the
noncoordinated counterions have been omitted for clarity.
Scheme 4. Synthesis of the Pt-Ag Cationic Complex 8
cis arrangement between the acetyl function and the olefin
is not readily accessible. Similar observations have been
made for the alcoholysis of related acetylpalladium systems,
which only took place in cases where the acetyl and alcohol
ligands are mutually cis.18 There appears to be no precedent
for an isolated complex resulting from olefin insertion into
a Pt-acetyl bond, and this is not too surprising when
considering the lower reactivity of Pt(II) complexes as
compared to their Pd(II) analogues which readily catalyze
CO/olefin copolymerization,19 and whose stability is some-
times sufficient to allow isolation of key metallacyclic
intermediates.12a,20
In one experiment, an excess of AgOTf was used to
abstract the chloride ligand from 5, and we noted a slight
change of the signals for the CHPh and PPh2 nuclei in H
and 31P{1H} NMR spectra, respectively, when compared to
the values for 6, suggesting the formation of a new complex.
The reaction was repeated using 2 equiv of AgOTf, and this
new complex could then be obtained in quantitative spec-
troscopic yield (31P{1H} NMR monitoring). It was isolated
and fully characterized by X-ray diffraction as the heterodi-
metallic Pt-Ag complex ([PtMe(κ2-PPO){µ-(η1-P;η1-O)-
1
PPO)}Ag(OTf)(Pt-Ag)]OTf)2 (8‚OTf)2 (Figure 5, Table 3,
Scheme 4). Although the spectroscopic solution data indi-
cated again the presence of a mixture of diastereomers, the
single crystal used for X-ray analysis contained only the RR/
SS diastereomers.
The crystal structure determination revealed the existence
in the solid state of a centrosymmetric, tetranuclear complex
based on two heterodinuclear Pt-Ag moieties linked by
triflate bridges. Whereas one of the Pt-bound PPO ligands
has remained chelated around the Pt(II) center, the other has
turned from dangling to bridging between the platinum and
silver centers, forming a six-membered ring, with a dative
PdOfAg+ bond of 2.234(5) Å. Interestingly, a Pt-Ag
metal-metal interaction of 2.819(1) Å is present, whose
value is similar to the sum of the atomic radii (Pt, 1.295 Å;
(19) (a) Drent, E.; Budzelaar, P. H. M. Chem. ReV. 1996, 96, 663. (b)
Bianchini, C.; Meli, A. Coord. Chem. ReV. 2002, 225, 35. (c)
Robertson, R. A. M.; Cole-Hamilton, D. J. Coord. Chem. ReV. 2002,
225, 67. (d) Bianchini, C.; Meli, A.; Oberhauser, W. Dalton Trans.
2003, 2627. (e) Nakano, K.; Kosaka, N.; Hiyama, T.; Nozaki, K.
Dalton Trans. 2003, 4039.
(20) Braunstein, P.; Durand, J.; Knorr, M.; Strohmann, C. Chem. Commun.
2001, 211.
1396 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
Scheme 5. Possible Intramolecular Rearrangements of Monomeric
8‚OTf in Solution
Ag, 1.339 Å), but larger than the sum of the ionic radii (Pt,
0.80 Å; Ag, 1.26 Å).21 This distance is in the range found
for complexes displaying a Pt(II)-Ag(I) interaction: a search
in CSD resulted in a median value around 2.8 Å for an upper
limit chosen for the Pt-Ag distance of 3.1 Å (CSD version
5.25). Another interesting feature is that in complex (8‚OTf)2
the Pt-Ag bond is almost perpendicular to the Pt-plane,
which allows a better overlap between the filled Pt(II) 5dz2
and the vacant silver orbitals. This square-based pyramidal
geometry around the Pt center is typical for complexes with
only one Pt-Ag bond and no bridging ligand covalently
bonded to Pt and Ag.22 Although numerous Pt(II)-Ag(I)
complexes involving penta- or hexacoordinated platinum
have been reported, there seems to be only one other
structurally characterized dinuclear, metal-metal-bonded
complex with an oxygen donor bridging ligand,23 and none
involving PdO donors.
The bridging triflate anions interact with the silver cations
at distances of 2.261(6) and 2.471(5) Å, representing the
formally covalent and dative bonds, respectively. To the best
of our knowledge, there are only 10 other cases where a
Ag-OTf bond is shorter or equal to 2.26 Å (CSD version
5.25).24 The other two triflate anions do not interact with
the cationic complex. It is difficult to say whether the solid-
state structure is fully retained in solution, in particular if
heterodi- or tetranuclear complexes are present and/or in
equilibrium. Breaking of the dimeric structure could result
from coordination of the second triflate in solution. A sharp
singlet was observed in 19F{1H} NMR, which could result
from fast exchange on the NMR time-scale between coor-
dinated and uncoordinated triflates or to magnetic equiva-
lence due to coordination of both triflates to Ag+ in a
heterodinuclear structure. The broad 31P{1H} NMR resonance
observed at room temperature for the PdO nuclei is
consistent with a chemical exchange involving these nuclei.
At least two possibilities can be envisaged (Scheme 5):
migration of the Pt-bound PdO donor to silver with triflate
migration from silver to platinum or a mutual, intramolecular
exchange between the Pt- and Ag-bonded ligands. Unfor-
tunately, the low-temperature 31P{1H} NMR spectra of 8‚
OTf were too complicated to be readily interpreted. Low-
temperature 195Pt{1H} NMR measurements showed an
increasing broadening of the signal down to 183 K, prevent-
ing detection of J(Pt-Ag) coupling. Therefore, the dynamic
exchanges sketched in Scheme 5 remain speculative.
Recently, dimetallic Pt/Ag systems have been employed
in the hydroarylation of unactivated arenes and olefins under
mild conditions.25 These systems are not monomolecular but
consist of a mixture of a Pt(II)-Cl complex and AgX (X )
BF4, OTf), and investigations showed that the role of the
silver salts clearly extended beyond simple chloride abstrac-
tion. In the alkoxycarbonylation reaction with acetyl-Pd-
(II) complexes,18 the intermediates in the precatalyst acti-
vation by chloride abstraction were found to contain Pd-
Ag-Cl moieties. This is in agreement with our own recent
studies on the reactivity of various halide abstractors, which
surprisingly led to the isolation and structural characterization
of an unprecedented Cl-Pt-Tl complex.26
Attempts to prepare dimetallic Pt-Tl or Pt-Au complexes
related to 8 were unfortunately not successful. In contrast to
the reaction with a second equivalent AgOTf, no reaction
was observed between complex 6, prepared from 5 and
TlPF6, and a second equivalent of TlPF6. After mixing the
compounds in an NMR tube using CDCl3 as solvent, TlPF6
remained undissolved even after 1 day and no change was
observed in the 31P{1H} NMR spectrum. The reaction
between 6‚BF4 and [Au(BF4)(tht)] (tht ) tetrahydrothiophene)
in CH2Cl2 at -60 °C also did not lead to the formation of a
dimetallic compound, but rather to some decomposition of
the gold precursor and formation of the mononuclear
complex [PtMe(tht)(κ2-PPO)]BF4 (9‚BF4), which was also
synthesized directly (see Experimental Section). According
to the values of the 1J(Pt-P) coupling constant of 4012 Hz,
the PPh2 group in this complex must be cis to the methyl
ligand. The remaining Au precursor was complexed by two
PPO ligands to yield [Au(κ1-PPO)2]BF4 (10‚BF4), whose
direct synthesis was carried out for comparison by a one-
pot synthesis from [AuCl(tht)] and PPO (see Experimental
(21) Holleman, A. F.; Wiberg, E. Lehrbuch der Anorganischen Chemie;
de Gruyter: Berlin-New York, 1985; pp 1032 and 1210.
(22) Fornie´s, J.; Mart´ın, A. In Metal Clusters in Chemistry; Braunstein,
P., Oro, L. A., Raithby, P. R., Eds.; Wiley-VCH: Weinheim, 1999;
Vol. 3, p 431 and references therein.
(23) Kozitsyna, N. Yu.; Ellern, A. M.; Struchkov, Yu. T.; Moiseev, I. Yu.
MendeleeV Commun. 1992, 100.
(24) (a) Braunstein, P.; Gomes Carneiro, T. M.; Matt, D.; Tiripicchio, A.;
Tiripicchio Camellini, M. Angew. Chem., Int. Ed. Engl. 1986, 25, 748.
(b) Allshouse, J.; Haltiwanger, R. C.; Allured, V.; DuBois, M. R. Inorg.
Chem. 1994, 33, 2505. (c) Gudat, D.; Schrott, M.; Bajorat, V.; Nieger,
M.; Kotila, S.; Fleischer, R.; Stalke, D. Chem. Ber. 1996, 129, 337.
(d) Gudat, D.; Holderberg, A. W.; Kotila, S.; Nieger, M. Chem. Ber.
1996, 129, 465. (e) Janssen, M. D.; Herres, M.; Zsolnai, L.; Spek, A.
L.; Grove, D. M.; Lang, H.; van Koten, G. Inorg. Chem. 1996, 35,
2476. (f) Terroba, R.; Hurtshouse, M. B.; Laguna, M.; Mendia, A.
Polyhedron 1999, 18, 807. (g) Bardaji, M.; Crespo, O.; Laguna, A.;
Fischer, A. K. Inorg. Chim. Acta 2000, 304, 7. (h) Wang, Q.-M.; Mak,
T. C. J. Am. Chem. Soc. 2000, 122, 7608. (i) Xu, X.; Nieuwenhuyzen,
M.; James, S. L. Angew. Chem., Int. Ed. 2002, 41, 764.
(25) Karshtedt, D.; Bell, A. T.; Tilley, T. D. Organometallics 2004, 23,
4169.
(26) Oberbeckmann-Winter, N.; Braunstein, P.; Welter, R. Organometallics
2004, 23, 6311.
Inorganic Chemistry, Vol. 44, No. 5, 2005 1397

Oberbeckmann-Winter et al.
in D2O) as external standards with downfield shifts reported as
positive. Alternatively, 1H and 31P{1H} NMR spectra were recorded
on Bruker Avance 500 and 400 instruments at 500.13 and 202.46
MHz or 400.13 and 161.98 MHz, respectively. The 195Pt{1H} NMR
spectra were recorded on the Bruker Avance 400 at 86.02 MHz
using H6PtCl6 in D2O as external standard. All NMR spectra were
measured at 298 K, unless otherwise specified. The assignment of
the signals was made by 1H,1H-COSY and 1H,13C-HMQC experi-
ments. IR spectra in the range of 4000-400 cm-1 were recorded
as KBr pellets on a FT-IR IFS66 Bruker spectrometer. Elemental
C, H, and N analyses were performed by the “Service de
microanalyses”, Universite´ Louis Pasteur, Strasbourg and at the
“Chemisches Laboratorium” of the Universita¨t Freiburg.
Section). Similar to compound 5, 10‚BF4 was obtained as a
mixture of two pairs of diastereomers, but its 31P{1H} NMR
spectrum contains two closely spaced triplets for the mutually
trans PPh2 groups, and two triplets for the PdO groups.
Attempts were made to simulate the spectrum of this AA′XX′
spin system (A ) A′ ) P; X ) X′ ) P(O)) by using the
program Win-Daisy.27 Assuming very small, not detectable
JAX′ and JA′X coupling constants, a large coupling constant
for the mutually trans PPh2 nuclei was obtained (JAA′ ) 772
Hz) and a small intra-ligand coupling constant (JAX ) JA′X′
) 18 Hz). The pattern of the signals changes to two singlets
for the related Pt(II) complex 5, because in this case the intra-
ligand coupling constant (JAX ) JA′X′) was also too small to
be detected.
-
When BF4 was used as a counterion, the 19F{1H} spectra
provided the appropriate signal with the pattern typical for B10-
F19 and B11-F19 shifts.28 The following compounds were synthe-
sized according to literature procedures: [PtClMe(cod)],29 [(diphen-
ylphosphinophenyl)methyl]phosphonic acid diethyl ester (PPO),6
and [AuCl(tht)].30 Other chemicals were commercially available
and used as received. All yields given are based on Pt.
Preparation and Spectroscopic Data for [PtClMe(K2-PPO)]
(1). Solid [PtClMe(cod)] (0.34 g, 0.96 mmol) and PPO (0.40 g,
0.97 mmol) were dissolved in CH2Cl2 (25 mL), and the resulting
solution was stirred for approximately 3 h at room temperature.
The volatiles were then removed in vacuo (to remove liberated
COD), and the residue was redissolved in CH2Cl2. This sequence
was repeated until complete conversion has occurred (7 days). The
crude product was obtained as a colorless powder, which was
washed with diethyl ether (10 mL) followed by pentane (20 mL)
and dried again in vacuo to afford 1 (0.59 g, 0.90 mmol, 94%).
Suitable single crystals for X-ray analysis were obtained at room
temperature by slow diffusion of pentane into a solution in CH2-
Conclusion
We have shown that the â-phosphonato-phosphine ligand
rac-Ph2PCH(Ph)P(O)(OEt)2 (abbreviated PPO) can display
hemilabile behavior in Pt(II) alkyl or acyl complexes when
two such functional ligands show a trans-arrangement of their
phosphine functions. The carbonylation of the methyl
complex 6‚OTf under 1 atm of CO leads to Pt(II) acetyl
complex 7, which is stable toward decarbonylation. As shown
by the reactions of 5 and 2 equiv of Ag+ or of 6‚OTf with
1 equiv of Ag+, the Pt(II) center is sufficiently electron-rich
to form a dimetallic Pt-Ag complex, (8‚OTf)2, whose crystal
structure revealed the dimeric nature in the solid state, with
two silver-bound triflates acting as bridging ligands. In
addition to the Ag-Pt bond, the Ag+ cation is stabilized by
a dative OfAg interaction involving one of the PPO ligands
of 6‚OTf, which has turned from terminal to bridging ligand.
In the context of reactivity studies, it is important to note
that typical chloride abstractors, such as Ag+, can compete
with the hard donor end of difunctional ligands and interfere
with their hemilabile behavior.
1
Cl2. IR: 1173 s cm-1 (νPdO). H NMR (CD2Cl2) δ: 0.74 (d, 3H,
3JP-H ) 3.6 Hz, 2JPt-H ) 88 Hz, PtCH3), 1.08 (dt, 3H, 3JH-H ) 7.0
4
3
Hz, JP-H ) 0.8 Hz, POCH2CH3), 1.10 (dt, 3H, JH-H ) 7.0 Hz,
4JP-H ) 0.7 Hz, POCH2CH3), 3.90-4.30 (overlapping m, 4H,
2
P(OCH2CH3)2), 4.32 (dd, 1H, JP-H ) 21.1 and 13.1 Hz, CHPh),
7.10-7.60 (m, 13H, aryl-CH), 7.85-7.95 (m, 2H, aryl-CH). 13C-
{1H} NMR (CD2Cl2) δ: -24.4 (d, JP-C ) 6.9 Hz, JPt-C ) 742
2
1
3
3
Hz, PtCH3), 16.0 (d, JP-C ) 6.6 Hz, POCH2CH3), 16.1 (d, JP-C
) 5.9 Hz, POCH2CH3), 44.6 (dd, JP-C ) 140.1 and 21.4 Hz,
1
2
CHPh), 65.0/66.4 (2 d, JP-C ) 7.4 Hz, P(OCH2CH3)2), 123.9 (d,
1JP-C ) 60.9 Hz, 3JP(O)-C ) 4.2 Hz, ipso-aryls, PPh2), 127.8-128.8
2
(m, aryl-CH), 129.8 (t, JP-C ) 5.8 Hz, ipso-aryl, CHPh), 130.4/
130.5 (2 d, 3JP-C ) 8.1 Hz, m-aryls, PPh2), 131.8/132.1 (2 d, 4JP-C
2
3
) 2.7 Hz, p-aryls, PPh2), 133.6 (d, JP-C ) 11.3 Hz, JPt-C ) 35
Hz, o-aryl, PPh2), 136.2 (d, 2JP-C ) 12.2 Hz, 3JPt-C ) 48 Hz, o-aryl,
PPh2). 31P{1H} NMR (CD2Cl2) δ: 14.2 (d, 2+3JP-P ) 36 Hz, 1JPt-P
The study of the interactions between square-planar Pt-
(II) complexes and cationic Ag(I) complexes is relevant to
the activation or properties of homogeneous catalysts involv-
ing these metals,18,25 and it is clear that typical chloride
abstractors, such as Ag+, do not always merely behave in
this way.
2+3
2+3
) 4661 Hz, PPh2), 42.6 (d,
J
) 36 Hz,
J
) 78 Hz,
P-P
Pt-P
P(O)). 195Pt{1H} NMR (CD2Cl2) δ: -4132 (1JP-Pt ) 4634 Hz,
2+3
J
) 77 Hz). Anal. Calcd for C24H29ClO3P2Pt (657.97): C,
P-Pt
43.81; H, 4.44. Found: C, 43.49; H, 4.27.
Preparation and Spectroscopic Data for [Pt{C(O)Me}Cl(K2-
PPO)] (2). A solution of [PtClMe(κ2-PPO)] (1) (0.30 g, 0.46 mmol)
in CH2Cl2 (25 mL) was placed under CO (1 atm) and stirred for 5
h at room temperature. Removing all volatiles in vacuo and
purification of the product by recrystallization from CH2Cl2/pentane
(2/1) at 5 °C yielded 2 as a pale green solid (0.28 g, 0.41 mmol,
89%), mostly as single crystals suitable for X-ray structure analysis.
IR: 1662 s (νCO), 1175 m cm-1 (νPdO). 1H NMR (CDCl3) δ: 1.08
Experimental Section
General Procedures. All manipulations were carried out under
inert dinitrogen atmosphere, using standard Schlenk-line conditions
and dried and freshly distilled solvents. The 1H, 1H{31P}, 13C{1H},
19F{1H}, and 31P{1H} NMR spectra were recorded unless otherwise
stated on a Bruker Avance 300 instrument at 300.13, 75.47, 282.40,
and 121.49 MHz, respectively, using TMS, CFCl3, or H3PO4 (85%
(28) Kuhlmann, K.; Grant, D. M. J. Phys. Chem. 1964, 68, 3208.
(29) Clark, H. C.; Manzer, H. C. J. Organomet. Chem. 1973, 59, 411.
(30) Uson, R.; Laguna, A.; Laguna, M. Inorg. Synth. 1989, 26, 85.
(27) Win-Daisy, Version 4.05; Bruker-Franzen Analytics GmbH, Bremen/
University of Du¨sseldorf, Germany, 1995.
1398 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
3
4
(dt, 3H, JH-H ) 7.1 Hz, JP-H ) 0.8 Hz, POCH2CH3), 1.11 (dt,
was added in one portion. A white precipitate formed immediately,
and the mixture was stirred at room temperature for 2 h. Celite
(0.5 g) was added to the reaction mixture, stirring was continued
for 15 min, and the solution was filtered. Removing the solvent in
vacuo afforded the product as an off-white powder (0.26 g, 0.34
mmol, 85%). Suitable single crystals for X-ray analysis were
obtained from a solution in CH2Cl2/toluene (3/1) by slowly
removing the solvents under reduced pressure. IR: 1171 s cm-1
(νPdO). 1H NMR (CD2Cl2) δ: 0.78 (d, 3H, 3JP-H ) 1.2 Hz, 2JPt-H
3
4
3H, JH-H ) 7.1 Hz, JP-H ) 0.6 Hz, POCH2CH3), 2.08 (s, 3H,
C(O)CH3), 3.90-4.20 (overlapping m, 4H, POCH2CH3), 4.30 (dd,
1H, JP-H ) 22.3 and 13.5 Hz, CHPh), 7.00-7.20 (m, 7H, aryl-
2
CH), 7.25-7.55 (m, 6H, aryl-CH), 7.85-7.95 (m, 2H, aryl-CH).
13C{1H} NMR (CDCl3) δ: 15.9 (d, 3JP-C ) 6.9 Hz, POCH2CH3),
3
3
16.0 (d, JP-C ) 6.2 Hz, POCH2CH3), 41.2 (d, JP-C ) 4.2 Hz,
1
C(O)CH3), 44.7 (dd, JP-C ) 138.4 and 20.1 Hz, CHPh), 64.7/
66.0 (2 d, 2JP-C ) 7.6 Hz, P(OCH2CH3)2), 123.5 (dd, 1JP-C ) 61.6
3
3
4
Hz, JP(O)-C ) 3.5 Hz, ipso-aryls, PPh2), 127.3-129.8 (m, aryls
and ipso-aryl), 130.2/130.3 (2 d, JP-C ) 8.3 Hz, m-aryls, PPh2),
) 77 Hz, PtCH3), 1.14 (dt, 3H, JH-H ) 7.1 Hz, JP-H ) 0.6 Hz,
3
3
4
POCH2CH3), 1.17 (dt, 3H, JH-H ) 7.1 Hz, JP-H ) 0.5 Hz,
POCH2CH3), 4.05-4.25 (overlapping m, 4H, P(OCH2CH3)2), 4.59
4
2
131.5/132.1 (2 d, JP-C ) 2.8 Hz, p-aryls, PPh2), 133.0 (d, JP-C
) 11.1 Hz, o-aryl, PPh2), 136.1 (d, 2JP-C ) 12.5 Hz, o-aryl, PPh2),
(dd, 1H, JP-H ) 22.7 and 14.3 Hz, CHPh), 7.05-7.30 (m, 7H,
2
190.1 (d, JP-C ) 5.2 Hz, C(O)CH3). 31P{1H} NMR (CDCl3) δ:
aryl-CH), 7.40-7.52 (m, 3H, aryl-CH), 7.55-7.65 (m, 3H, aryl-
2
12.2 (d, 2+3JP-P ) 35 Hz, 1JPt-P ) 5086 Hz, PPh2), 39.9 (d, 2+3JP-P
CH), 7.80-7.95 (m, 2H, aryl-CH). H NMR (500.13 MHz, CD2-
1
2+3
) 35 Hz,
J
) 51 Hz, P(O)). 195Pt{1H} NMR (CDCl3) δ:
Cl2) selected data δ: 0.76 (d, 3H, 3JP-H ) 1.1 Hz, 2JPt-H ) 78 Hz,
Pt-P
-3457 (dd, 1JP-Pt ) 5066 Hz, 2+3JP-Pt ) 50 Hz). Anal. Calcd for
C25H29ClO4P2Pt (685.98): C, 43.77; H, 4.26. Found: C, 43.76; H,
4.291.
PtCH3), 4.54 (dd, 1H, 2JP-H ) 22.7 and 14.2 Hz, CHPh). 1H{31P}
2
NMR (500.13 MHz, CD2Cl2) selected data δ: 0.76 (s, 3H, JPt-H
) 78 Hz, PtCH3), 4.54 (br s, 1 H, CHPh). 13C{1H} NMR (CD2-
2
1
Preparation and Spectroscopic Data for [PtMe(CO)(K2-PPO)]-
OTf (3‚OTf). Solid [Pt{C(O)Me}Cl(κ2-PPO)] (2) (0.16 g, 0.23
mmol) was dissolved in CH2Cl2 (20 mL), and solid AgOTf (0.06
g, 0.23 mmol) was added in one portion. A white precipitate formed
immediately, and the mixture was stirred at room temperature for
1.5 h. Celite (0.5 g) was added to the reaction mixture, stirring
was continued for 15 min, and the solution was filtered. Removing
the solvent in vacuo afforded the product as an off-white powder
(0.15 g, 0.19 mmol, 83%). IR: 2093 m (νCO), 1166 s cm-1 (νPdO).
Cl2) δ: -20.3 (d, JP-C ) 6.7 Hz, JPt-C ) 727 Hz, PtCH3), 16.0
3
3
(d, JP-C ) 6.4 Hz, POCH2CH3), 16.1 (d, JP-C ) 6.2 Hz,
1
POCH2CH3), 44.0 (dd, JP-C ) 140.2 and 26.0 Hz, CHPh), 66.0
(d, 2JP-C ) 7.5 Hz, POCH2CH3), 66.8 (d, 2JP-C ) 7.8 Hz, POCH2-
1
1
CH3), 120.6 (br q, JF-C ) 316.5 Hz, CF3), 122.8 (dd, JP-C
68.8 Hz, JP(O)-C ) 2.7 Hz, ipso-aryl, PPh2), 126.6 (dd, JP-C
)
)
3
1
3
66.6 Hz, JP-C ) 4.8 Hz, ipso-aryl, PPh2), 128.2-129.7 (m, aryls
and ipso-aryl), 130.5 (d, 3JP-C ) 7.8 Hz, m-aryls, PPh2), 130.6 (d,
3JP-C ) 7.9 Hz, m-aryls, PPh2), 132.5 (d, JP-C ) 2.8 Hz, p-aryl,
4
4
2
1H NMR (CDCl3) δ: 1.08 (dt, 3H, JH-H ) 7.1 Hz, JP-H ) 0.9
Hz, POCH2CH3), 1.10 (dt, 3H, JH-H ) 7.1 Hz, JP-H ) 1.1 Hz,
3
4
PPh2), 132.9 (d, JP-C ) 2.5 Hz, p-aryl, PPh2), 133.3 (d, JP-C
)
11.1 Hz, 3JPt-C ) 38 Hz, o-aryl, PPh2), 136.2 (d, 2JP-C ) 11.9 Hz,
3JPt-C ) 56 Hz, o-aryl, PPh2). 19F{1H} NMR (CD2Cl2) δ: -78.3
(s, CF3). 31P{1H} NMR (CD2Cl2) δ: 9.9 (d, 2+3JP-P ) 27 Hz, 1JPt-P
3
4
3
4
POCH2CH3), 1.43 (dd, 3H, JP-H ) 7.4 Hz, JP(O)-H ) 0.5 Hz,
2JPt-H ) 48 Hz, PtCH3), 4.12/4.24 (2 dq, 4H, 2JP-H ) 7.2 Hz, 3JH-H
2+3
2+3
2
) 5360 Hz, PPh2), 41.0 (d,
J
) 27 Hz,
J
) 120 Hz,
) 7.1 Hz, P(OCH2CH3)2), 5.85 (dd, 1H, JP-H ) 19.4 and 13.7
P-P
Pt-P
1
P(O)). 195Pt{1H} NMR (CD2Cl2) δ: -4258 (br d, JP-Pt ) 5363
Hz). Anal. Calcd for C25H29F3O6P2PtS (771.60): C, 38.92; H, 3.79;
S, 4.16. Found: C, 38.85; H, 3.57; S, 3.67.
Hz, 3+4JPt-H ) 8 Hz, CHPh), 7.05-7.70 (m, 13H, aryl-CH), 8.00-
1
8.15 (m, 2H, aryl-CH). H NMR (CD2Cl2) selected data δ: 5.32
2
3+4
1
(dd, 1H, JP-H ) 13.4 and 20.4 Hz,
J
) 8 Hz, CHPh). H-
Pt-H
{31P} NMR (CDCl3) selected data δ: 1.08/1.10 (2 t, 2 × 3H, 3JH-H
In-Situ Reaction between [PtMe(OTf)(K2-PPO)] (4) and
NCMe. Solid [PtMe(OTf)(κ2-PPO)] (4) (0.03 g, 0.04 mmol) was
dissolved in NCMe (5 mL). After the mixture was stirred for 30
min, the solvent was removed in vacuo and the residue was
redissolved in CD2Cl2 (0.5 mL). NMR data for [PtMe(NCMe)(κ2-
2
) 7.1 Hz, P(OCH2CH3)2), 1.43 (s, 3H, JPt-H ) 48 Hz, PtCH3),
3
4.12/4.24 (2 q, JH-H ) 7.1 Hz, 4H, P(OCH2CH3)2), 5.85 (br s,
1H, CHPh). 13C{1H} NMR (CDCl3) δ: 4.9 (dd, 2JP-C ) 74.0 Hz,
3JP(O)-C ) 4.7 Hz, PtCH3), 15.6/15.7 (2 d, JP-C ) 6.8 Hz,
3
P(OCH2CH3)2), 36.9 (dd, 1JP-C ) 130.4 and 13.8 Hz, CHPh), 67.6
1
3
PPO)]OTf, H NMR (CD2Cl2) δ: 0.70 (d, 3H, JP-H ) 2.9 Hz,
(d, 2JP-C ) 7.8 Hz, POCH2CH3), 68.2 (d, 2JP-C ) 7.7 Hz, POCH2-
2JPt-H ) 82 Hz, PtCH3), 1.09 (t, 3H, 3JH-H ) 7.0 Hz, POCH2CH3),
1
1
3
4
CH3), 120.9 (br q, JF-C ) 318.9 Hz, CF3), 124.4 (dd, JP-C
)
)
1.10 (dt, 3H, JH-H ) 7.0 Hz, JP-H ) 0.7 Hz, POCH2CH3), 2.53
(s, 3H, NCCH3), 3.95-4.20 (m, 4H, P(OCH2CH3)2), 4.49 (dd, 1H,
2JP-H ) 20.9 and 14.1 Hz, CHPh), 7.10-7.30 (m, 7H, aryl-CH),
7.30-7.45 (m, 3H, aryl-CH), 7.55-7.65 (m, 3H, aryl-CH), 7.85-
8.00 (m, 2H, aryl-CH). 13C{1H} NMR (CD2Cl2) δ: -23.7 (d, 2JP-C
) 6.9 Hz, 1JPt-C ) 700 Hz, PtCH3), 3.8 (s, NCCH3), 15.9/16.0 (2
3
1
49.8 Hz, JP(O)-C ) 7.0 Hz, ipso-aryl, PPh2), 125.2 (dd, JP-C
49.8 Hz, 3JP(O)-C ) 4.8 Hz, ipso-aryl, PPh2), 127.1 (t, 2JP-C ) 5.7
Hz, ipso-aryl, CHPh), 128.5-129.3/129.8-130.1 (2 m, aryls),
3
4
130.6/130.7 (2 d, JP-C ) 7.7 Hz, m-aryls, PPh2), 132.7 (d, JP-C
4
) 2.8 Hz, p-aryl, PPh2), 132.9 (d, JP-C ) 2.3 Hz, p-aryl, PPh2),
133.8 (d, 2JP-C ) 12.6 Hz, 3JPt-C ) 12 Hz, o-aryl, PPh2), 135.1 (d,
3
1
d, JP-C ) 6.2 Hz, P(OCH2CH3)2), 43.0 (dd, JP-C ) 138.4 and
2JP-C ) 13.1 Hz, JPt-C ) 14 Hz, o-aryl, PPh2), 158.9 (dd, JP-C
3
2
2
24.2 Hz, CHPh), 65.9/67.1 (2 d, JP-C ) 7.6 Hz, P(OCH2CH3)2),
) 7.5 Hz, JP(O)-C ) 3.3 Hz, CdO). 19F{1H} NMR (CDCl3) δ:
3
1
121.3 (br q, JF-C ) 320.8 Hz, CF3), 121.0-126.5 (m, ipso-aryls
-78.5 (s, CF3). 31P{1H} NMR (CDCl3) δ: 34.0 (d,
J
) 74
2+3
and CH3CN), 128.3 (t, 2JP-C ) 5.5 Hz, ipso-aryl, CHPh), 128.5-
P-P
Hz, 1JPt-P ) 1294 Hz, PPh2), 59.3 (d, 2+3JP-P ) 74 Hz, 2+3JPt-P
)
)
129.9 (m, aryls), 130.5/130.6 (2 d, 3JP-C ) 7.6 Hz, m-aryls, PPh2),
47 Hz, P(O)). 195Pt{1H} NMR (CDCl3) δ: -4111 (br d, JP-Pt
1
4
2
132.8/133.0 (2 d, JP-C ) 2.8 Hz, p-aryls, PPh2), 133.8 (d, JP-C
3
2
1297 Hz). Anal. Calcd for C26H29F3O7P2PtS (799.60): C, 39.06;
H, 3.66. Found: C, 38.69; H, 4.04.
) 11.8 Hz, JPt-C ) 39 Hz, o-aryl, PPh2), 136.0 (d, JP-C ) 11.8
Hz, JPt-C ) 51 Hz, o-aryl, PPh2). 19F{1H} NMR (CD2Cl2) δ: )
3
-79.1 (s, CF3). 31P{1H} NMR (CD2Cl2) δ: 12.9 (d, 2+3JP-P ) 33
Alternatively, the product can be synthesized in quantitative
spectroscopic yield by stirring a solution of 4 for 2 h under CO (1
atm) (NMR tube experiment).
Hz, 1JPt-P ) 4828 Hz, PPh2), 44.5 (d, 2+3JP-P ) 33 Hz, 2+3JPt-P
)
108 Hz, P(O)). 195Pt{1H} NMR (CD2Cl2) δ: -4365 (br d, JP-Pt
1
Preparation and Spectroscopic Data for [PtMe(OTf)(K2-
PPO)] (4). Solid [PtClMe(κ2-PPO)] (1) (0.26 g, 0.40 mmol) was
dissolved in CH2Cl2 (30 mL), and solid AgOTf (0.11 g, 0.43 mmol)
) 4837 Hz).
In-Situ Reaction between [PtMe(OTf)(K2-PPO)] (4) and C2H4.
Solid [PtMe(OTf)(κ2-PPO)] (4) (0.03 g, 0.04 mmol) was dissolved
Inorganic Chemistry, Vol. 44, No. 5, 2005 1399

Oberbeckmann-Winter et al.
in CD2Cl2 (0.5 mL) and exposed to C2H4 (1 atm) for 1 h. Selected
Alternatively, the product can be synthesized in quantitative
spectroscopic yield by addition of 1 equiv of PPO to a solution of
1 in CD2Cl2 and stirring for 2.5 days (NMR tube experiment).
1
NMR data for [PtMe(C2H4)(κ2-PPO)]OTf, H NMR (CD2Cl2) δ:
3
2
0.70 (d, 3H, JP-H ) 3.8 Hz, JPt-H ) 83 Hz, PtCH3), 1.09 (br t,
3H, 2JH-H ) 6.5 Hz, POCH2CH3), 1.11 (br t, 3H, 2JH-H ) 6.8 Hz,
POCH2CH3), 3.95-4.20 (m, 4H, P(OCH2CH3)2), 4.89 (dd, 1H,
2JP-H ) 20.8 and 14.4 Hz, CHPh), 5.39 (s, free and coordinated
ethylene), 7.05-7.35 (m, 9H, aryl-CH), 7.45-7.55 (m, 1H, aryl-
CH), 7.55-7.70 (m, 3H, aryl-CH), 7.85-8.00 (m, 2H, aryl-CH).
19F{1H} NMR (CD2Cl2) δ: -79.0 (s, CF3). 31P{1H} NMR (CD2-
Preparation and Spectroscopic Data for [PtMe(K2-PPO)(K1-
PPO)]BF4 (6‚BF4). Solid [PtClMe(κ2-PPO)2] (5) (0.58 g, 0.54
mmol) was dissolved in CH2Cl2 (30 mL), and AgBF4 (0.11 g, 0.57
mmol) was added in one portion. A white precipitate formed
immediately, and the mixture was stirred at room temperature for
1 h. Celite (0.5 g) was added to the reaction mixture, stirring was
continued for 15 min, and the solution was filtered. Removing the
solvent in vacuo afforded the product as a mixture of diastereomers
in the form of an off-white powder (0.53 g, 0.47 mmol, 87%). IR:
2+3
1
Cl2) δ: 19.4 (d,
J
) 40 Hz, JPt-P ) 4335 Hz, PPh2), 46.2
P-P
2+3
2+3
(d,
J
) 40 Hz,
J
) 73 Hz, P(O)).
P-P
Pt-P
Preparation and Spectroscopic Data for trans-[PtClMe(K1-
1
1250 m (νPdO), 1162 s cm-1 (νPdO, coord.). H NMR (CDCl3) δ:
PPO)2] (5). Solid [PtClMe(cod)] (0.35 g, 1.00 mmol) and PPO
(0.83 g, 2.01 mmol) were dissolved in CH2Cl2 (25 mL), and the
resulting solution was stirred for 3 h at room temperature. Removing
all volatiles in vacuo, washing the residue with a mixture of diethyl
ether/pentane (1/5, 25 mL) followed by pentane (20 mL), and drying
in vacuo afforded 5 as a colorless powder (1.01 g, 0.94 mmol, 94%).
A mixture of diastereomers was obtained, and suitable single
crystals for X-ray analysis were obtained from a solution in CH2-
Cl2/pentane (2/1) by slowly removing the solvents under reduced
pressure for the CH2Cl2 adduct of the RS,SR diastereomer. IR: 1249
0.30/0.32 (2 t, 2 × 3H, 3JP-H ) 6.6 Hz, 2JPt-H ) 88 Hz, 2 PtCH3),
3
4
1.00/1.01 (2 dt, 2 × 6H, JH-H ) 7.0 Hz, JP-H ) 0.6 Hz, 2
3
P(OCH2CH3)2), 1.06/1.08 (2 t, 2 × 6H, JH-H ) 7.0 Hz, 2
P(OCH2CH3)2), 3.70-4.10 (overlapping m, 2 × 8H, 4 P(OCH2-
CH3)2), 4.93 (d of virtual t, 2H, 2JP(O)-H ) 22.5 Hz, | JP-H + 4JP-H
|
2
) 10.8 Hz, 2 CHPh), 4.95 (d of virtual t, 2H, 2JP(O)-H ) 22.6 Hz,
2
4
| JP-H + JP-H| ) 11.0 Hz, 2 CHPh), 7.10-7.35 (m, 28H, aryl-
CH), 7.40-7.55 (m, 16H, aryl-CH), 7.55-7.65 (m, 8H, aryl-CH),
7.85-7.95 (m, 8H, aryl-CH). 19F{1H} NMR (CDCl3) δ: -152.7
(s, BF4). 31P{1H} NMR (CDCl3) δ: 29.4 (t, JP-P ) 19 Hz, JPt-P
1
1
s cm-1 (νPdO). H NMR (CDCl3) δ: -0.43/-0.39 (2 t, 2 × 3H,
) 3174 Hz, PPh2), 29.6 (t, JP-P ) 20 Hz, 1JPt-P ) 3180 Hz, PPh2),
2
3
3JP-H ) 6.6 Hz, JPt-H ) 77 Hz, 2 PtCH3), 0.85 (t, 6H, JH-H
)
35.5 (br, P(O)). 195Pt{1H} NMR (CDCl3) δ: -4386 (br t, 1JP-Pt
)
7.0 Hz, P(OCH2CH3)2), 0.91/0.94 (2 t, 2 × 6H, 3JH-H ) 7.2 Hz, 2
P(OCH2CH3)2), 1.08 (t, 6H, 3JH-H ) 7.0 Hz, P(OCH2CH3)2), 3.55-
4.15 (overlapping m, 2 × 8H, 4 P(OCH2CH3)2), 6.20 (d of virtual
3157 Hz), -4392 (br t, 1JP-Pt ) 3180 Hz). Anal. Calcd for C47H55-
BF4O6P4Pt (1121.73): C, 50.33; H, 4.94. Found: C, 50.29; H, 5.22.
Preparation and Spectroscopic Data for [PtMe(K2-PPO)(K1-
PPO)]OTf (6‚OTf). This product was synthesized from 5 by
addition of 1 equiv of solid AgOTf to a solution of 5 in CH2Cl2
and stirring for 1 h. The workup was similar to that for 6‚BF4, and
the product was isolated in 85% yield. The ratio of diastereomers
2
2
4
t, 2H, JP(O)-H ) 26.6 Hz, | JP-H + JP-H| ) 12.6 Hz, 2 CHPh),
2
2
4
6.22 (d of virtual t, 2H, JP(O)-H ) 24.2 Hz, | JP-H + JP-H| )
12.2 Hz, 2 CHPh), 6.95-7.35 (m, 44H, aryl-CH), 7.50-7.55/7.60-
7.65 (2 m, 2 × 4H, aryl-CH), 7.90-7.95/8.05-8.10 (2 m, 2 ×
1
4H, aryl-CH). H NMR (500.13 MHz, CD2Cl2) δ: -0.46 (t, 3H,
1
(as determined by H NMR resonance of the Pt-Me group) was
2
3
3JP-H ) 6.6 Hz, JPt-H ) 80 Hz, PtCH3), -0.44 (t, 3H, JP-H
)
2:1 directly after the reaction, but 1:1 after 2 days. 1H NMR (CD2-
2
3
6.5 Hz, JPt-H ) 80 Hz, PtCH3), 0.95 (dt, 6H, JH-H ) 7.0 Hz,
3
2
Cl2) δ: 0.35 (t, 3H, JP-H ) 6.7 Hz, JPt-H ) 89 Hz, PtCH3,
4JP-H ) 0.5 Hz, P(OCH2CH3)2), 1.01 (dt, 6H, JH-H ) 7.1 Hz,
3
diastereomer 1), 0.36 (t, 3H, 3JP-H ) 6.7 Hz, 2JPt-H ) 89 Hz, PtCH3,
diastereomer 2), 1.01 (dt, 6H, JP-H ) 0.7 Hz, JH-H ) 7.0 Hz, 2
POCH2CH3, diastereomer 1), 1.02 (dt, 6H, JP-H ) 0.5 Hz, JH-H
) 7.0 Hz, 2 POCH2CH3, diastereomer 2), 1.06 (dt, 6H, JP-H
4JP-H ) 0.7 Hz, P(OCH2CH3)2), 1.03/1.14 (2 t, 2 × 6H, JH-H
)
3
2
3
7.1 Hz, 2 P(OCH2CH3)2), 3.65-4.15 (overlapping m, 2 × 8H, 4
2
3
2
P(OCH2CH3)2), 6.13 (d of virtual t, 2 × 2H, JP(O)-H ) 25.9 Hz,
2
)
2
4
| JP-H + JP-H| ) 11.2 Hz, 4 CHPh), 7.05-7.10 (m, 8H, aryl-
CH), 7.15-7.20 (m, 16H, aryl-CH), 7.25-7.35 (m, 8H, aryl-CH),
7.35-7.45 (m, 12H, aryl-CH), 7.50-7.55/7.60-7.65 (2 m, 2 ×
4H, aryl-CH), 7.90-7.95/8.05-8.10 (2 m, 2 × 4H, aryl-CH). 1H-
{31P} NMR (500.13 MHz, CD2Cl2) selected data δ: -0.46/
3
0.7 Hz, JH-H ) 7.0 Hz, 2 POCH2CH3, diastereomer 1), 1.08 (dt,
6H, 2JP-H ) 0.5 Hz, 3JH-H ) 7.0 Hz, 2 POCH2CH3, diastereomer
2), 3.70-4.10 (overlapping m, 2 × 8H, 4 P(OCH2CH3)2), 4.71 (d
of virtual t, 2H, 2JP(O)-H ) 22.7 Hz, | JP-H + 4JP-H| ) 10.7 Hz, 2
2
2
CHPh, diastereomer 2), 4.72 (d of virtual t, 2H, JP(O)-H ) 22.9
2
-0.45 (2 s, 2 × 3H, JPt-H ) 81 Hz, PtCH3), 0.95/1.01/1.03/1.14
2
4
Hz, | JP-H + JP-H| ) 10.7 Hz, 2 CHPh, diastereomer 1), 7.20-
3
(4 t, 4 × 6H, JH-H ) 7.0 Hz, 4 P(OCH2CH3)2), 6.13 (br s, 2 ×
7.40 (m, 28H, aryl-CH), 7.45-7.60 (m, 24H, aryl-CH), 7.80-7.90
2H, 4 CHPh). 13C{1H} NMR (CDCl3) δ: -10.8/-10.1 (2 t, 2JP-C
(m, 8H, aryl-CH). H{31P} NMR (CD2Cl2) selected data δ: 0.35
1
3
) 5.3 Hz, PtCH3), 15.4/15.5/15.6/15.9 (4 d, JP-C ) 5.6 Hz, 4
(s, 3H, 2JPt-H ) 89 Hz, PtCH3, diastereomer 1), 0.36 (s, 3H, 2JPt-H
P(OCH2CH3)2), 39.2 (d of virtual t, 1JP(O)-C ) 133.4 Hz, | JP-C
+
3
1
) 89 Hz, PtCH3, diastereomer 2), 1.01 (t, 6H, JH-H ) 7.0 Hz, 2
3JP-C| ) 15.6 Hz, 2 CHPh), 40.4 (d of virtual t, JP(O)-C ) 132.8
3
1
POCH2CH3, diastereomer 1), 1.02 (t, 6H, JH-H ) 7.0 Hz, 2
Hz, | JP-C + 3JP-C| ) 17.4 Hz, 2 CHPh), 61.3/61.7/62.2/62.4 (4 d,
1
POCH2CH3, diastereomer 2), 4.71 (br s, 2 × 2H, 4 CHPh). 13C-
2JP-C ) 6.8 Hz, 4 P(OCH2CH3)2), 126.4-128.0 (m, aryls), 129.4
(d, JP-C ) 13.0 Hz, aryl-CH, PPh2), 130.0 (d, JP-C ) 15.5 Hz,
{1H} NMR (CD2Cl2) δ: -20.6/-20.2 (2 t, JP-C ) 5.2 Hz, JPt-C
2
1
3
) 717 Hz, 2 PtCH3), 16.0/16.1/16.1/16.2 (4 d, JP-C ) 6.2 Hz, 4
aryl-CH, PPh2), 131.7 (br s, p-aryls, PPh2), 133.4 (dd, 2JP-C ) 40.3
P(OCH2CH3)2), 42.2/42.3 (2 d virtual t, 1JP(O)-C ) 136.3 Hz, | JP-C
1
2
3
2
and 21.1 Hz, ipso-aryls, CHPh), 133.9/134.2 (2 virtual t, | JP-C
+
+
+ JP-C| ) 16.6 Hz, 4 CHPh), 64.4/64.5 (2 d, JP-C ) 6.9 Hz, 4
POCH2CH3), 65.3/65.4 (2 d, 2JP-C ) 7.6 Hz, 4 POCH2CH3), 121.4
(br q, 1JF-C ) 321.1 Hz, CF3), 124.5-125.7/126.3-127.5 (2 br m,
ipso-aryls, PPh2), 128.5-129.5 (2 m, aryls), 130.1-130.6 (m, ipso-
aryls, CHPh), 131.3-131.6/132.1-132.4 (2 m, aryls, PPh2), 134.7/
4JP-C| ) 11.4 Hz, o-aryls, PPh2), 136.4/136.7 (2 virtual t, | JP-C
2
4JP-C| ) 13.6 Hz, o-aryls, PPh2). 31P{1H} NMR (CDCl3) δ: 23.1
3
3
(s, JPt-P ) 45 Hz, P(O)), 23.5 (s, JPt-P ) 82 Hz, P(O)), 32.8 (s,
1JPt-P ) 3250 Hz, PPh2), 32.9 (s, JPt-P ) 3242 Hz, PPh2). 195Pt-
1
{1H} NMR (CDCl3) δ: -4582 (tt, JP-Pt ) 3239 Hz, JP-Pt ) 82
1
3
134.9 (2 virtual t, | JP-C + 4JP-C| ) 14.1 Hz, o-aryls, PPh2), 135.6/
2
1
3
135.7 (2 virtual t, | JP-C + 4JP-C| ) 13.9 Hz, o-aryls, PPh2). 19F{1H}
2
Hz), -4580 (tt, JP-Pt ) 3237 Hz, JP-Pt ) 44 Hz). Anal. Calcd
for C47H55ClO6P4Pt (1070.38): C, 52.74; H, 5.18. Found: C, 52.47;
H, 5.27.
NMR (CD2Cl2) δ: -79.2 (s, CF3). 31P{1H} NMR (CD2Cl2) δ: 29.0
(t, JP-P ) 20 Hz, 1JPt-P ) 3175 Hz, PPh2, diastereomer 2), 29.3 (t,
1400 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
1
2
4
JP-P ) 19 Hz, JPt-P ) 3194 Hz, PPh2, diastereomer 1), 34.9 (br,
| JP-H + JP-H| ) 11.8 Hz, 2 CHPh), 7.15-7.30 (m, 20H, aryl-
CH), 7.35-7.45 (m, 8H, aryl-CH), 7.50-7.60 (m, 24H, aryl-CH),
P(O)). 31P{1H} NMR (161.98 MHz, C2D2Cl4, 383 K) δ: 29.7 (t,
JP-P ) 18.3 Hz, 1JPt-P ≈ 3200 Hz, PPh2), 29.8 (t, JP-P ) 17.6 Hz,
1JPt-P ≈ 3200 Hz, PPh2), 34.3 (t, JP-P ) 17.2 Hz, P(O)), 34.4 (t,
JP-P ) 18.4 Hz, P(O)). 31P{1H} NMR (202.46 MHz, CD2Cl2, 187
K) δ: 20.0 (s, P(O), noncoord.), 21.6 (s, P(O), noncoord.), spin
system ABMX (A ) B ) P, M ) P(O), X ) Pt), 24.1 (dd, 2JA-B
≈ 415 Hz, 2JA-M ) 45 Hz, 1JA-X ≈ 3000 Hz, PPh2, chelated ligand,
diastereomer 2), 24.4 (dd, 2JA-B ≈ 430 Hz, 2JA-M ) 47 Hz, 1JA-X
≈ 3150 Hz, PPh2, chelated ligand, diastereomer 1), 31.1 (d, 2JA-B
7.75-7.90 (m, 8H, aryl-CH). H{31P} NMR (CD2Cl2, select.) δ:
1
0.49/0.52 (2 s, 2 × 3 H, 2JPt-H ) 87 Hz, 2 PtCH3), 4.82/4.97 (2 br
s, 2 × 2H, 4 CHPh). 13C{1H} NMR (CD2Cl2) δ: -20.3 (t, 2JP-C
)
5.2 Hz, PtCH3), -19.3 (t, 2JP-C ) 4.8 Hz, PtCH3), 15.9/16.0/16.1/
16.2 (4 d, 3JP-C ) 6.2 Hz, 4 P(OCH2CH3)2), 41.8/42.0 (2 d of virtual
t, 1JP(O)-C ) 135.6 Hz, | JP-C + 3JP-C| ) 16.6 Hz, 4 CHPh), 64.9/
1
2
65.2/65.3/65.4 (4 d, JP-C ) 7.6 Hz, 4 P(OCH2CH3)2), 121.2 (q,
1JF-C ) 320.4 Hz, CF3), 123.5-127.0 (m, ipso-aryls, PPh2), 128.7-
130.2 (m, aryls and ipso-aryl), 131.2-131.6/132.1-132.8 (2 m,
2
1
) 422 Hz, JB-M ≈ 0 Hz, JB-X ≈ 3240 Hz, 2 PPh2, nonchelated
ligand), 48.0 (br, P(O), coord., diastereomer 2), 49.6 (br, P(O),
coord., diastereomer 1). 195Pt{1H} NMR (CD2Cl2): δ ) -4388
aryls), 134.0/134.5 (2 virtual t, | JP-C + 4JP-C| ) 12.4 Hz, o-aryls,
2
PPh2), 135.8/136.2 (2 virtual t, | JP-C + 4JP-C| ) 13.8 Hz, o-aryls,
2
1
1
(br t, JP-Pt ) 3171 Hz), -4394 (br t, JP-Pt ) 3175 Hz).
PPh2). 19F{1H} NMR (CD2Cl2) δ: -78.7 (s, CF3). 31P{1H} NMR
(CD2Cl2) δ: 27.8 (t, JP-P ) 19 Hz, 1JPt-P ) 3036 Hz, PPh2), 28.9
Preparation and Spectroscopic Data for [Pt{C(O)Me}(K2-
PPO)(K1-PPO)]BF4 (7‚BF4). A solution of [PtMe(κ2-PPO)(κ1-
PPO)]BF4 (6‚BF4) (0.34 g, 0.30 mmol) in CH2Cl2 (25 mL) was
placed under CO (1 atm) and stirred for 4 h at room temperature.
Removing all volatiles in vacuo and purification by precipitation
with pentane yielded a mixture of diastereomers 7‚BF4 as a white
(t, JP-P ) 18 Hz, JPt-P ) 3066 Hz, PPh2), 34.3 (br, P(O)). 195Pt-
1
{1H} NMR (CD2Cl2) δ: -4299 (br t, JP-Pt ≈ 2990 Hz), -4301
1
1
(br t, JP-Pt ≈ 3050 Hz). Anal. Calcd for C49H55AgF6O12P4PtS2
(1440.93): C, 40.84; H, 3.85; S, 4.45. Found: C, 40.92; H, 3.64;
S, 4.14.
Alternatively, the product can be synthesized in quantitative
spectroscopic yield (31P{1H} NMR) by addition of 1 equiv of
AgOTf to a CH2Cl2 solution of 6‚OTf and stirring for 2 h.
Reaction between [Au(BF4)(tht)] and 6‚BF4. Solid [AuCl(tht)]
(0.10 g, 0.31 mmol) in CH2Cl2 (10 mL) was cooled to -60 °C,
and AgBF4 (0.06 g, 0.31 mmol) was added in one portion. The
mixture was stirred for 2 h at -60 °C, and then the precipitate was
allowed to settle. The filtered solution of [Au(BF4)(tht)] was added
via cannula to a solution of [PtMe(κ2-PPO)(κ1-PPO)]BF4 (6‚BF4)
(0.33 g, 0.29 mmol) in CH2Cl2 (10 mL) at -60 °C. The mixture
was stirred for 3 h while kept at this temperature. Removing the
solvent in vacuo was followed by extraction of the residue at -60
°C with CH2Cl2. NMR spectra showed the existence of a mixture
of [PtMe(tht)(κ2-PPO)]BF4 (9‚BF4) and [Au(κ1-PPO)2]BF4 (10‚BF4).
A crystalline powder of one diastereomer of 10‚BF4 with 0.5 equiv
of CH2Cl2 could be obtained by repeated crystallization at 5 °C
from a solution in CH2Cl2 layered with pentane. IR: 1248 s cm-1
solid (0.31 g, 0.27 mmol, 90%). IR: 1658 s (νCO), 1250 s (νPdO
,
1
noncoord.), 1163 s cm-1 (νPdO, coord.). H NMR (CDCl3) δ: )
2
3
0.95/1.00 (2 dt, 2 × 6H, JP-H ) 0.7 Hz, JH-H ) 7.1 Hz, 2
P(OCH2CH3)2), 1.09 (s, 3H, C(O)CH3), 1.10/1.11 (2 t, 2 × 6H,
3JH-H ) 7.1 Hz, 2 P(OCH2CH3)2), 1.36 (s, 3H, C(O)CH3), 3.50-
3.90 (overlapping m, 8H, 4 P(OCH2CH3)2), 4.95 (d of virtual t,
2
2H, 2JP(O)-H ) 25.1 Hz, | JP-H + 4JP-H| ) 12.8 Hz, 2 CHPh), 5.01
2
(d of virtual t, 2H, 2JP(O)-H ) 24.0 Hz, | JP-H + 4JP-H| ) 12.3 Hz,
2 CHPh), 7.10-7.55 (m, 44H, aryl-CH), 7.60-7.80 (m, 8H, aryl-
CH), 7.85-8.00 (m, 8H, aryl-CH). 1H{31P} NMR (CDCl3) selected
data δ: 4.95/5.01 (2 br s, 4H, 4 CHPh). 13C{1H} NMR (CDCl3) δ:
3
15.7/15.8/15.9/16.0 (4 d, JP-C ) 6.5 Hz, 4 P(OCH2CH3)2), 41.6/
1
41.7 (2 d of virtual t, 1JP(O)-C ) 134.0 Hz, | JP-C + 3JP-C| ) 17.3
Hz, 4 CHPh), 41.6 (t, 3JP-C ) 5.8 Hz, C(O)CH3), 41.9 (t, 3JP-C
)
2
5.6 Hz, C(O)CH3), 64.1/64.3/64.4/64.6 (4 d, JP-C ) 7.6 Hz, 4
P(OCH2CH3)2), 125.0-126.1 (m, ipso-aryls, PPh2), 127.7-129.0
(m, aryls), 129.2-129.6 (m, ipso-aryls, CHPh), 130.9-132.1 (m,
2
aryls), 134.6/134.9/135.1/135.6 (4 virtual t, | JP-C + 4JP-C| ) 13.8
1
3
(νPdO, noncoord.). H NMR (CDCl3) δ: 0.87 (t, 6H, JH-H ) 7.1
Hz, 2 POCH2CH3), 0.90 (dt, 6H, 3JP-H ) 1.6 Hz, 3JH-H ) 7.1 Hz,
2 POCH2CH3), 3.60-3.95 (overlapping m, 8H, 2 P(OCH2CH3)2),
2
Hz, o-aryls, PPh2), 196.1 (t, JP-C ) 5.3 Hz, C(O)CH3), 196.9 (t,
2JP-C ) 5.1 Hz, C(O)CH3). 19F{1H} NMR (CDCl3) δ: -152.4 (s,
1
BF4). 31P{1H} NMR (CDCl3) δ: 25.4 (t, JP-P ) 16 Hz, JPt-P
)
2
2
4
5.03 (d of virtual t, 2H, JP(O)-H ) 20.9 Hz, | JP-H + JP-H| )
10.4 Hz, 2 CHPh), 5.30 (s, 1H, CH2Cl2), 7.10-7.20/7.35-7.45 (2
m, 2 × 7H, aryl-CH), 7.55-7.65/7.70-7.75/7.85-7.95/8.15-8.25
1
3638 Hz, PPh2), 26.0 (t, JP-P ) 17 Hz, JPt-P ) 3624 Hz, PPh2),
33.3 (br, P(O)). 195Pt{1H} NMR (CDCl3) δ: -3662 (br t, 1JP-Pt
)
3630 Hz), -3674 (br t, 1JP-Pt ) 3620 Hz). Anal. Calcd for C48H55-
1
(4 m, 4 × 4H, aryl-CH). H{31P} NMR (CDCl3) selected data δ:
0.87/0.90 (2 t, 2 × 6H, 3JH-H ) 7.1 Hz, 2 P(OCH2CH3)2), 5.03 (s,
BF4O7P4Pt (1149.74): C, 50.14; H, 4.82. Found: C, 49.89; H, 5.18.
2H, 2 CHPh). 13C{1H} NMR (CDCl3) δ: 15.8/15.9 (2 d, JP-C
)
3
Preparation and Spectroscopic Data for [PtMe(K2-PPO){µ-
(η1-P;η1-O)PPO)}Ag(OTf)(Pt-Ag)]OTf (8‚OTf). Solid [PtClMe-
(κ2-PPO)2] (5) (0.35 g, 0.33 mmol) was dissolved in CH2Cl2 (30
mL), and solid AgOTf (0.17 g, 0.66 mmol) was added in one
portion. A white precipitate was formed immediately, and the
mixture was stirred at room temperature for 2 h. Celite (0.5 g) was
added to the reaction mixture, stirring was continued for 15 min,
and the solution was filtered. Removing the solvent in vacuo
afforded the product as an off-white powder (0.43 g, 0.30 mmol,
91%). This mixture of diastereomers was redissolved in CH2Cl2/
toluene (3/1), and slow removal of the solvents under reduced
pressure afforded suitable single crystals for X-ray analysis of the
RR,SS diastereomer. IR: 1262 s cm-1 (νPdO, coord. to Pt). 1H NMR
6.2 Hz, 2 P(OCH2CH3)2), 43.5 (d of virtual t, 1JP(O)-C ) 134.9 Hz,
1
3
| JP-C + JP-C| ) 11.8 Hz, 2 CHPh), 53.4 (CH2Cl2), 62.5/64.3 (2
2
d, JP-C ) 7.7 Hz, 2 P(OCH2CH3)2), 126.2-130.1 (m, aryls),
131.1-131.5 (m, aryls), 132.3/132.7 (2 s, p-aryls, PPh2), 134.5/
2
4
135.2 (2 virtual t, | JP-C + JP-C| ) 16.0 Hz, o-aryls, PPh2). 19F-
{1H} NMR (CDCl3) δ: -152.9 (s, BF4). 31P{1H} NMR (CDCl3)
δ: 21.0 (t, JP-P ) 9.0 Hz, P(O)), 50.6 (t, JP-P ) 9.0 Hz, PPh2).
Anal. Calcd for C46H52AuBF4O6P4‚0.5CH2Cl2 (1151.05): C, 48.52;
H, 4.64. Found: C, 48.12; H, 4.79.
Preparation and Spectroscopic Data for [PtMe(tht)(K2-PPO)]-
BF4 (9‚BF4). Solid [PtClMe(cod)] (0.15 g, 0.48 mmol) and PPO
(0.17 g, 0.48 mmol) were dissolved in CH2Cl2 (20 mL), and then
THT (ca. 0.5 mL) and solid AgBF4 (0.10 g, 0.51 mmol) were added.
A white precipitate formed immediately, and the mixture was stirred
at room temperature for 2 h. Celite (0.5 g) was added to the reaction
mixture, stirring was continued for 15 min, and the solution was
filtered. Removing the solvent in vacuo afforded the product as a
3
2
(CD2Cl2) δ: 0.50/0.54 (2 t, 2 × 3H, JP-H ) 6.6 Hz, JPt-H ) 87
3
Hz, 2 PtCH3), 1.01/1.02/1.08/1.16 (4 t, 4 × 6H, JH-H ) 7.0 Hz,
4 P(OCH2CH3)2), 3.80-4.20 (overlapping m, 2 × 8H, 4 P(OCH2-
CH3)2), 4.84 (d of virtual t, 2H, 2JP(O)-H ) 23.6 Hz, | JP-H + 4JP-H
|
2
) 11.4 Hz, 2 CHPh), 4.99 (d of virtual t, 2H, 2JP(O)-H ) 24.7 Hz,
Inorganic Chemistry, Vol. 44, No. 5, 2005 1401

Oberbeckmann-Winter et al.
Table 4. Selected Crystallographic Data for Complexes 1, 2, 4, 5‚CH2Cl2, and (8‚OTf)2
1
2
4
5‚CH2Cl2
(8‚OTf)2
formula
C24H29ClO3P2Pt
C25H29ClO4P2Pt
C25H29F3O6P2PtS
C47H55ClO6P4Pt,
CH2Cl2
C98H110Ag2F12O24P8Pt2S4
fw
657.95
685.96
771.57
1155.26
2881.78
cryst system
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
orthorhombic
Aba2
32.453(5)
17.774(2)
8.834(1)
orthorhombic
P212121
11.8980(3)
13.3110(3)
16.5850(4)
monoclinic
C2/c
16.876(2)
10.482(1)
33.257(5)
triclinic
P-1
triclinic
P-1
11.260(5)
13.878(5)
16.347(5)
90.352(5)
102.141(5)
101.173(5)
2447(2)
13.550(5)
14.827(5)
15.009(5)
90.958(5)
109.643(5)
94.520(5)
2828(2)
90.87(5)
5096(1)
8
2626.6 (1)
4
5882(1)
8
2
1
crystal size
(mm3)
color
0.10 × 0.08 × 0.06
0.12 × 0.10 × 0.08
0.12 × 0.10 × 0.08
0.10 × 0.10 × 0.10
0.13 × 0.10 × 0.08
colorless
1.715
5.760
173(2)
2576
pale green
1.735
5.594
173(2)
1344
off-white
1.742
5.006
173(2)
3024
colorless
1.568
3.208
173(2)
1164
colorless
1.692
3.081
173(2)
1432
D
calc (g cm-3
)
µ (mm-1
T (K)
)
F(000)
Θ limits (deg)
no. of data
measured
no. of data
(I > 2σ(I))
no. of
0.997/30.04
3940
0.998/27.47
5751
0.972/30.01
8340
0.988/30.06
14 307
0.996/30.04
16 464
2551
271
5139
292
6467
337
12 766
559
13 584
658
parameters
flack param.
R
-0.006(8)
0.0347
0.0318
0.0401
0.0322
0.0499
Rw
0.0755
0.0815
0.1057
0.0811
0.1381
GOF
0.871
0.871
1.133
0.990
1.124
max/min res.
1.484/-1.047
0.848/-1.183
3.513/-2.028
2.254/-2.085
1.829/-1.848
dens. (e Å-3
)
2
2
4
colorless powder (0.35 g, 0.44 mmol, 92%). IR: 1163 s cm 1 (νPd
O). 1H NMR (CDCl3) δ: 0.53 (d, 3H, 3JP-H ) 3.8 Hz, 2JPt-H ) 71
t, 2H, JP(O)-H ) 20.7 Hz, | JP-H + JP-H| ) 10.3 Hz, 2 CHPh),
-
2
2
4
5.03 (d of virtual t, 2H, JP(O)-H ) 20.9 Hz, | JP-H + JP-H| )
10.4 Hz, 2 CHPh), 7.00-8.40 (overlapping m, 2 × 30H, aryl-CH).
3
Hz, PtCH3), 1.06/1.08 (2 t, 6H, JH-H ) 7.0 Hz, P(OCH2CH3)2),
2.08 (br s, 4H, SCH2CH2), 3.13 (br s, 4H, SCH2CH2), 4.00-4.20
(m, 4H, P(OCH2CH3)2), 4.85 (dd, 1H, JP-H ) 21.0 and 13.9 Hz,
1H{31P} NMR (CDCl3) selected data δ: 5.01/5.03 (2 s, 2 × 2H, 2
× 2 CHPh). 13C{1H} NMR (CDCl3) δ: 15.7/15.8 (2 d, JP-C
)
2
3
3+4
J
) 23 Hz, CHPh), 7.05-7.25 (m, 7H, aryl-CH), 7.30-
6.8 Hz, 4 P(OCH2CH3)2), 42.5-44.7 (overlapping m, 4 CHPh),
Pt-H
7.45 (m, 3H, aryl-CH), 7.50-7.60 (m, 3H, aryl-CH), 7.90-8.00
62.5/62.6 (2 d, 2JP-C ) 7.4 Hz, 2 P(OCH2CH3)2), 64.3 (d, 2JP-C
)
(m, 2H, aryl-CH). 13C{1H} NMR (CDCl3) δ: -23.2 (br s, 1JPt-C
)
7.4 Hz, 2 P(OCH2CH3)2), 126.0-136.0 (overlapping m, aryls). 19F-
{1H} NMR (CDCl3) δ: -152.9 (s, BF4). 31P{1H} NMR (CDCl3)
δ: 21.0 (t, JP-P ) 9.0 Hz, P(O)), 21.1 (t, JP-P ) 9.7 Hz, P(O)),
50.2 (t, JP-P ) 9.7 Hz, PPh2), 50.6 (t, JP-P ) 9.0 Hz, PPh2).
3
718 Hz, PtCH3), 15.8/15.9 (2 d, JP-C ) 6.2 Hz, P(OCH2CH3)2),
28.0 (s, tht), 30.8 (s, tht), 41.8 (dd, JP-C ) 137.7 and 20.1 Hz,
CHPh), 65.7/66.3 (2 d, JP-C ) 7.6 Hz, P(OCH2CH3)2), 121.9-
1
2
125.8 (m, ipso-aryls), 128.1-129.5 (m, aryls), 130.4/130.5 (2 d,
3JP-C ) 8.3 Hz, m-aryls, PPh2), 132.1/132.5 (2 d, 4JP-C ) 2.8 Hz,
p-aryls, PPh2), 133.6 (d, 2JP-C ) 11.8 Hz, 3JPt-C ) 31 Hz, o-aryl,
X-ray Collection and Structure Determinations. The diffrac-
tion data were collected on a Nonius Kappa-CCD area detector
diffractometer (Mo KR, λ ) 0.71070 Å; φ scan). The relevant data
were summarized in Table 4. The cell parameters were determined
from reflections taken from one set of 10 frames (1.0° steps in φ
angle), each at 20 s exposure. The structures were solved using
direct methods (SHELXS97) and refined against F2 using the
SHELXL97 software. The absorption was corrected empirically
(with Sortav) for compounds 1, 2, 4, 5‚CH2Cl2, and (8‚OTf)2.31
All non-hydrogen atoms were refined with anisotropic parameters.
The hydrogen atoms were included in their calculated positions
and refined with a riding model in SHELXL97.32
2
3
PPh2), 135.9 (d, JP-C ) 12.4 Hz, JPt-C ) 42 Hz, o-aryl, PPh2).
19F{1H} NMR (CDCl3) δ: -153.5 (s, BF4). 31P{1H} NMR (CDCl3)
2+3
1
δ: 18.4 (d,
J
) 36 Hz, JPt-P ) 4012 Hz, PPh2), 45.9 (d,
P-P
2+3
J
P-P
) 36 Hz, 2+3JPt-P ) 63 Hz, P(O)). 195Pt{1H} NMR (CDCl3)
δ: -4342 (dd, JP-Pt ) 4000 Hz,
1
2+3
J
) 66 Hz). Anal. Calcd
P-Pt
for C28H37BF4O3P2PtS (797.50): C, 42.17; H, 4.68. Found: C,
42.34; H, 4.91.
Preparation and Spectroscopic Data for [Au(K1-PPO)2]BF4
(10‚BF4). Solid [AuCl(tht)] (0.10 g, 0.31 mmol) and PPO (0.26 g,
0.63 mmol) were dissolved in CH2Cl2 (10 mL), and AgBF4 (0.06
g, 0.31 mmol) was added in one portion. The mixture was stirred
for 2 h at room temperature, and then the precipitate was allowed
to settle. Filtration and removal of the volatiles afforded a colorless
powder, which was found to be a diastereomeric mixture of the
product (0.31 g, 0.28 mmol, 90%). The following spectroscopic
assignments are consistent with the data obtained for one of the
diastereomers of 10‚BF4 (see above). IR: 1248 s cm-1 (νPdO). 1H
NMR (CDCl3) δ: 0.84-0.94 (m, 2 × 6H, 4 P(OCH2CH3)2), 3.60-
3.95 (overlapping m, 2 × 8H, 4 P(OCH2CH3)2), 5.01 (d of virtual
Acknowledgment. This work was supported by the
CNRS and the Ministe`re de la Recherche. We are grateful
to the European Commission for support in the COST D-30
Action and for a Marie Curie fellowship (HPMF-CT-2002-
01659), and also to the French Embassy in Berlin and the
(31) Blessing, R. H. Crystallogr. ReV. 1987, 1, 3.
(32) Sheldrick, G. M. SHELXL97, Program for the refinement of crystal
structures; University of Go¨ttingen, Germany, 1997.
1402 Inorganic Chemistry, Vol. 44, No. 5, 2005

Synthesis of Pt(II) Phosphonato-Phosphine Complexes
5‚CH2Cl2, and (8‚OTf)2. This material is available free of charge
via the Internet at http://pubs.acs.org. The crystallographic material
can also be obtained from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax, (44) 1223-
336-033; e-mail, deposit@ccdc.cam.ac.uk), deposition numbers
CCDC 252485-252489.
Ministe`re des Affaires Etrange`res (Paris) for a postdoctoral
grant to N.O.-W. We also wish to thank L. Allouche and C.
Huguenard for the simulation of the NMR spectra.
Supporting Information Available: Crystallographic informa-
tion files (CIF), variable-temperature 31P{1H} NMR and P,P-COSY
spectra of compound 6, and ORTEP plots for complexes 1, 2, 4,
IC0485559
Inorganic Chemistry, Vol. 44, No. 5, 2005 1403