Synthesis and characterisation of the platinum complexes [PtCl(CCl=PAr)(PPh3)2] and [PtCl(CCl=PAr′)(PPh 3)2] as potential intermediates in the preparation of phosphaalkynes

Article abstract of DOI:10.1016/j.jorganchem.2005.04.029

Oxidative addition reactions of Cl₂CPR (R = 2,4,6- tris(trifluoromethyl)phenyl (Ar) or 2,6-bis(trifluoromethyl)phenyl (Ar′) with Pt(PPh₃)₄ yield the cis and trans (at platinum) complexes [PtCl(ClCPAr)(PPh₃)₂] and [PtCl(ClCPAr′) (PPh₃)₂]. All starting materials and intermediates have been characterised by NMR spectroscopy. The crystal and molecular structures of the trans-platinum complexes have been determined by single-crystal X-ray diffraction at low temperature.

Full text of DOI:10.1016/j.jorganchem.2005.04.029

Journal of Organometallic Chemistry 690 (2005) 3630–3637
www.elsevier.com/locate/jorganchem
Synthesis and characterisation of the platinum
complexes [PtCl(CCl@PAr)(PPh3)2] and [PtCl(CCl@PAr0)(PPh3)2]
as potential intermediates in the preparation of phosphaalkynes
*
Stephanie M. Cornet, Keith B. Dillon , Andres E. Goeta, Judith A.K. Howard,
´
´
Mark D. Roden, Amber L. Thompson
Chemistry Department, University of Durham, South Road, Durham DH1 3LE, UK
Received 26 January 2005; received in revised form 6 April 2005; accepted 7 April 2005
Available online 29 June 2005
Abstract
Oxidative addition reactions of Cl2C@PR (R = 2,4,6-tris(trifluoromethyl)phenyl (Ar) or 2,6-bis(trifluoromethyl)phenyl (Ar0)
with Pt(PPh3)4 yield the cis and trans (at platinum) complexes [PtCl(ClC@PAr)(PPh3)2] and [PtCl(ClC@PAr0)(PPh3)2]. All starting
materials and intermediates have been characterised by NMR spectroscopy. The crystal and molecular structures of the trans-
platinum complexes have been determined by single-crystal X-ray diffraction at low temperature.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Platinum complexes; Crystal structures; NMR
1. Introduction
or transition metals is now well documented [11–16].
We recently reported the synthesis and characterisa-
tion of several group 13 [17], group 14 [18] and group
15 [19] compounds containing either one or two
Ar/Ar0/Ar00 (Ar00 = 2,4-(CF3)2C6H3) ligands, and several
other phosphorus compounds containing these bulky
substituents have been described in the literature
[2,11b,20–28].
In low-coordinate phosphorus chemistry, the fluo-
romesityl and fluoroxyl groups have been employed in
the synthesis of stable diphosphenes (ArP@PAr)
[12,20–23], iminophosphines ArP=NAr [24], phosphe-
nium salts ðArPNRþ2 Þ [25] and phosphides ArPRꢀ [26].
Surprisingly, only a few phosphaalkenes containing the
As the field of low-coordinate phosphorus chemistry
grows, research on multiply bonded phosphaalkenes
(P@C bond) and phosphaalkynes (P„C bond) is of
considerable interest, as many applications can be envis-
aged [1,2]. For example, phosphaalkenes have been em-
ployed as ligands in transition-metal-catalysed organic
reactions [3–7] and for the synthesis of new inorganic
polymers [8–10]. The use of bulky substituents on phos-
phorus has facilitated the development of several
synthetic routes to phosphaalkenes [2].
The chemistry of the bulky and electron-withdraw-
ing 2,4,6-(CF3)3C6H2 (fluoromes = Ar) and 2,6-
(CF3)2C6H3 (fluoroxyl = Ar0) substituents and their
ability to stabilise low-coordinate main group elements
2,4,6-(CF3)C6H2
group
have
been
described:
ArP@CCl2, ArP@C(SiMe3)H, ArP@C(H)Ph [27] and
ArP@CMe2 [28]. The only phosphaalkenes with the
2,6-(CF3)2C6H3 substituent, Ar0P@CMe2 and Ar0P@C-
MePh, have been reported very recently by Gates
et al. [28].
*
Corresponding author. Tel.: +44 191 3342092; fax: +44 191
3844737.
E-mail address: k.b.dillon@durham.ac.uk (K.B. Dillon).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.04.029

S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
3631
L3
Pd
Cl
PdL2Cl
Cl
Cl
PdL4
-L
R
P
C
R
P
C
R
P
C
L=PPh3
Cl
Cl
R = 2,4,6-tBu3C6H2
- PdL2Cl2
P
C
R
R
P
C
Scheme 1. Proposed mechanism for the synthesis of a phosphaalkyne using PdL4 and RP@CCl2.
Phosphorus–carbon double bonds can be seen as the
starting point for the formation of phosphaalkynes with
the ligands Ar or Ar0. Among the numerous routes
known to prepare phosphaalkynes [2], the synthesis
of Mes*C„P (Mes* = super-mes = 2,4,6-tris-tBu3C6H2)
by the reaction of the phosphaalkene Mes*P@CCl2 with
Pd(PPh3)4 was described by Romanenko et al. [29], with
a mechanism involving the rearrangement of the inter-
mediate species [RP„C:] (Scheme 1). It involves the
dechlorination of Cl2C@PR and the migration of the li-
gand R from phosphorus to carbon. Similar products
were observed by Angelici and coworkers from reactions
of phosphaalkenes with Pd(0) or Pt(0) complexes of
phosphanes [30], although in this case they described
the intermediate formation of a four-membered ring
between a C@C bond in the aryl ring and the P@C
phosphaalkene bond (Scheme 2).
our knowledge, no phosphaalkynes containing fluoro-
mes or fluoroxyl ligands have been reported. However,
some unsuccessful attempts at their synthesis have been
reported by Goodwin [31].
Using ‘‘AngeliciÕs method’’ in an attempt to prepare
phosphaalkynes containing either Ar or Ar0 ligands,
we report here the reaction between RP@CCl2 (R = Ar
or Ar0) and Pt(PPh3)4 to form the stable complexes
[PtCl(C(Cl)@PR)(PPh3)2], the trans-isomers of which
have been structurally characterised by single crystal
X-ray diffraction.
2. Results and discussion
The phosphaalkenes were prepared via reaction of
the phosphane ArPCl2 or a mixture of Ar0PCl2 and
Ar00PCl2 with a solution of CHCl2Li at ꢀ130 ꢁC to give
ArP(Cl)CHCl2 (1) and Ar0P(Cl)CHCl2 (2). Ar00PCl2
did not produce the intermediate compound
Ar00P(Cl)CHCl2, since the signals from the starting
material Ar00PCl2 were still visible in both 31P and
The chemistry of phosphaalkynes is diverse and work
has mainly been performed with aryl and alkyl substitu-
ents on the carbon atom. The alkyl groups used, such as
tBu, tend to be electron-donating ligands and increase
the electron density at the C„P triple bond. So far, to
X
PR'3
X
M
PR'3
X
M
R'3P
C
P
R'3P
M(PR'3)4
C
P
RP
CX2
tBu
R' = Et, Ph
M = Pt, Pd
X
R
But
tBu
+
[MX2(PPh3)2]
P
CR
(where X = Cl or Br)
Scheme 2. Mechanism demonstrated by Angelici et al.

3632
S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
BuLi
–130oC
CH2Cl2
CHCl2Li
4:1:1 pent:THF:Et2O
CF3
CF3
CHCl2Li
PCl(CHCl2)
R1
R1
PCl2
o
–
130 C
4:1:1 pent:THF:Et2O
CF3
CF3
DBU
-DBU.HCl
THF
CF3
P
CCl2
R1
CF3
R1 =H or CF3
Scheme 3. Synthesis of a phosphaalkene.
19F NMR spectra after reaction. 1,8-Diazabi-
cyclo[5.4.0]undec-7-ene (DBU) was then added to
RP(Cl)CHCl2 (R = Ar (1) or Ar0 (2)) solution at ꢀ78
ꢁC (Scheme 3) to give the phosphaalkenes ArP@CCl2
(3) or Ar0P@CCl2 (4), respectively. Purification by distil-
lation under reduced pressure led to a colourless oil in
both cases. NMR data for the products ArPCl2 [12,21],
Ar0PCl2 [20], ArP(Cl)CHCl2 (1), Ar0P(Cl)CHCl2 (2),
ArP@CCl2 (3) and Ar0P@CCl2 (4) are listed in Table 1.
Comparison of the chemical shifts with those of the
starting material ArPCl2 (or Ar0PCl2) shows that d19F
values are at lower frequency for the phosphaalkene
than for the phosphane, and that d31P moves to a higher
frequency. This implies more shielding and electron den-
sity on the CF3 groups. The electron-withdrawing effect
is facilitated by the formation of the phosphorus–carbon
double bond. The creation of this P@C bond decreases
the p-character of the phosphorus hybrid orbital. The
phosphorus becomes more positive and the chemical
shifts move to higher frequency. Simultaneously the
electron density in the trifluoromethyl groups increases,
moving the fluorine shifts to a lower frequency.
According to Angelici et al. [30], reaction of phos-
phaalkenes having two Cl substituents on carbon with
Pt(0) or Pd(0) compounds leads to an intermediate Pt
or Pd complex, which can undergo rearrangement to
give a phosphaalkyne (Scheme 2). In the present work,
addition of the phosphaalkene RP@CCl2 (R = Ar or
Ar0) to a Pt(PPh3)4 solution in toluene (or benzene) at
room temperature gave rise to a mixture of trans- and
cis-[PtCl(ClC@PR)(PPh3)2] (R = Ar for 5a (trans) or
5b (cis): R = Ar0 for 6a (trans) or 6b (cis)) (Fig. 1),
Table 1
31P and 19F NMR data for RPCl2, RP(Cl)CHCl2 and RP@CCl2 (R = Ar (2,4,6-(CF3)3C6H2) or Ar0 (2,6-(CF3)2C6H3))
d31
P
d19
F
o-CF3
p-CF3
4
145.6 (septet, JP–F 61.3)
4
ArPCl2
ArP(Cl)CHCl2 (1)
ArP@CCl2 (3)
ꢀ53.3 (d, JP–F 61.3)
ꢀ64.2
ꢀ64.5
ꢀ63.9
4
63.1 (septet, JP–F 49.3)
4
ꢀ55.3 (d, JP–F 49.3)
4
202.4 (septet, JP–F 20.6)
4
ꢀ60.0 (d, JP–F 21.1)
4
148.4 (septet, JP–F 61.3)
4
Ar0PCl2
Ar0P(Cl)CHCl2 (2)
Ar0P@CCl2 (4)
ꢀ53.2 (d, JP–F 61.3)
4
65.3 (septet, JP–F 48.8)
4
ꢀ53.9 (d, JP–F 48.9)
4
207.6 (septet, JP–F 20.7)
4
ꢀ59.6 (d, JP–F 21.1)
Chemical shifts are given in ppm and coupling constants in Hz.

S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
3633
Trans and cis [Pt(Cl)(RP=CCl)(PPh3)2]
iour was found for cis-isomer 6b (Table 2). The trans-
isomer 5a should exhibit a triplet of septets. The reso-
nance at 14.1 ppm for Pa in 5b appeared as a triplet
but should be a doublet of doublets. The coupling con-
stants JP–P (from Pb) and JP–P (from Pc) are very sim-
ilar in this instance, and separate couplings could not be
distinguished.
CF3
CF3
Cl
Cl
R1
Pc C
R1
Pc
Cl
C
PaPh3
PaPh3
PbPh3
2
3
Pt
Pt
Ph3Pa
CF3
Cl
CF3
The initial 31P NMR of the platinum complex con-
taining the Ar0 ligand exhibited signals assigned to the
cis-isomer 6b. Removing half of the solvent afforded a
white solid, which was isolated and displayed a reso-
nance with platinum satellites at 15.3 ppm (1JPt–P 3673
Hz), probably from cis-[Pt(PPh3)2Cl2] (d 13.5 ppm,
1JPt–P 3680 Hz [30]). Spectra were recorded regularly
for the filtrate, and resonances corresponding to the
trans-complex 6a were observed after two weeks. Sol-
vent was removed in vacuo, leaving a yellow/brown oil
which was dissolved in toluene. The 31P NMR spectrum
of this solution did not show the presence of the cis- and
trans-isomers, but new signals of low intensity were ob-
served: a multiplet at 131.5 and a peak at 26.4 ppm. No
platinum satellites were found, probably due to the low
intensity of the signals. The 19F NMR spectrum dis-
played a doublet at ꢀ58.6 ppm (4JP–F 8.1 Hz) and a
singlet at ꢀ63.2 ppm. These could arise from an
intermediate compound in the synthesis of a phos-
phaalkyne; a cyclic species such as the one characterised
by Angelici et al. [30] (Scheme 2) would require three
31P signals, however, since all three P atoms are
inequivalent.
cis-isomer
trans-isomer
5a R1=CF3
6a R1=H
5b R1=CF3
6b R1=H
Fig. 1. trans- and cis-[Pt(Cl)(RP@CCl)(PPh3)2].
identified from their 31P and 19F NMR data (Tables 2
and 3, respectively). It should be emphasised that some
of the values for coupling constants in Table 2 are
approximate, because of the low intensity and complex-
ity of the satellite signals. Resonances in the 19F NMR
spectra were assigned according to their relative intensi-
ties when compared with the 31P NMR spectra. A signal
for free PPh3 was also observed at ꢀ6 ppm in the 31P
spectra.
The multiplet in the phosphaalkene region for com-
plex 5b should, in fact, be a doublet of doublets of sep-
tets, due to coupling with the fluorines of the two o-CF3
groups (7 lines) and the phosphorus from the PPh3
3
groups. It was not possible to extract JP–P between Pa
and Pc, expected to be the smallest value, from the com-
plex spectrum observed for Pc, although an approximate
value was derived from the Pa resonance. Similar behav-
Table 2
31P NMR data for the platinum complexes (chemical shifts are given in ppm and coupling constants in Hz)
cis 5b
trans 5a
a
a
d
JPt–P
3JP–P
2JP–P
4JP–F
d
JPt–P
3JP–P
4JP–F
[PtCl(ClC@PAr)(PPh3)2]
Pa
Pb
Pc
14.1 (tb)
17.3 (dd)
198.1 (m)
4064
1897
376
15.3c
46.5
45.4
15.3c
16.8
24.1(d)
2963
29.0
24.4
203.7
512
NR
22.6
cis 6b
Pa
Pb
trans 6a
24.3(d)
[PtCl(ClC@PAr0)(PPh3)2]
13.5 (tb)
17.1 (dd)
202.4 (m)
4118
1935
412
18.7c
46.6
46.1
18.7c
16.7
2992
507
29.8
NR
Pc
22.3
208.6
24.1
NR = not resolved.
a
b
c
2
1JPt–Pa/b and JPt–Pc
Pseudo-triplet.
.
See text re coupling constants.
Table 3
19F NMR data for the platinum complexes (chemical shifts are given in ppm and coupling constants in Hz)
cis 5b and 6b
trans 5a and 6a
d
4JP–F
d
4JP–F
[PtCl(ClC@PAr)(PPh3)2]
[PtCl(ClC@PAr0)(PPh3)2]
o-CF3
p-CF3
ꢀ57.9
ꢀ63.0
ꢀ57.5
23.7
ꢀ58.3
ꢀ63.7
ꢀ58.0
23.0
o-CF3
23.0
23.7

3634
S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
The rate of isomerisation of the cis- to the trans-com-
plex was faster for compound 5, where both cis- and
trans-isomers could be observed in the solution NMR
spectra in the first instance, with possibly a slight excess
of the cis-complex. Chemical shifts for compounds 5a
and 6a, or 5b and 6b, are very similar. The 1JPt–P coupling
constants for 5a (2963 Hz) and 6a (2992 Hz), and for 5b
(4064 Hz) and 6b (4118 Hz), are typical of trans- and
cis-isomers, respectively. They may be compared with
the data of Angelici et al. [30] for trans-
[PtCl(CCl=PR)(PEt3)2] (2753 Hz) and its bromo-ana-
logue (2712 Hz), and for cis-[PtCl(ClC@PR)(PPh3)2],
observed as an intermediate (4203 Hz), where
R = 2,4,6-tBu3C6H2. Both trans-complexes 5a and 6a
were isolated (Section 3), and characterised by single crys-
tal X-ray diffraction at 120 and 150 K, respectively. Their
molecular structures are displayed in Figs. 2 and 3, while
selected bond distances and angles are listed in Table 4.
Both 5a and 6a crystallise in the triclinic space group
ꢀ
P1, with Z = 2. In both cases there is also one molecule
of solvent of crystallisation present in the unit cell (tol-
uene and dichloromethane for 5a and 6a, respectively).
The platinum adopts a square planar environment,
which is defined by the two PPh3 (in a trans-arrange-
ment), Cl and [ClC@PR] ligands. The atoms Pt, P(2),
P(3), Cl(1) and C(10) are nearly coplanar. The C(10)–
Fig. 3. The crystal structure of [Pt(Cl)(ClC@PAr0)(PPh3)2] (6a) with
selected atoms labelled. Displacement ellipsoids for the non-hydrogen
atoms are drawn at the 50% probability level.
Table 4
˚
Bond distances (A) and angles (ꢁ) for the two platinum complexes 5a
and 6a
˚
˚
P(1) distances (1.688(2) A in 5a, 1.688(4) A in 6a) are
the same within experimental error as those of the
C@P bonds in trans-[PtCl(ClC@PMes*)(PEt3)2]
5a
6a
˚
Bond distances (A)
˚
˚
(1.678(5) A) [30], Ph(Me3Si)C@PMes* (1.676(6) A)
Pt(1)–C(10)
Pt(1)–P(3)
Pt(1)–P(2)
Pt(1)–Cl(1)
P(1)–C(10)
P(1)–C(11)
Cl(11)–C(10)
2.014(2)
2.3203(4)
2.3286(4)
2.3629(5)
1.688(2)
1.873(2)
1.766(2)
2.022(4)
2.323(1)
2.334(1)
2.368(2)
1.688(4)
1.882(5)
1.773(4)
Bond angles (ꢁ)
C(10)–Pt(1)–P(3)
C(10)–Pt(1)–P(2)
P(3)–Pt(1)–P(2)
C(10)–Pt(1)–Cl(1)
P(3)–Pt(1)–Cl(1)
P(2)–Pt(1)–Cl(1)
P(1)–C(10)–Cl(11)
92.42(5)
93.94(5)
173.64(2)
177.65(5)
89.04(2)
84.61(2)
123.0(1)
92.6(1)
94.0(1)
173.38(4)
177.8(1)
89.27(5)
84.12(5)
122.1(3)
˚
[32] and Ph2C@PMes (1.692(3) A) [32]. Three short
contacts between the fluorine atoms of the o-CF3
groups and the phosphorus atom were found in both
structures: P(1)ꢁ ꢁ ꢁF(11) 3.039(2), P(1)ꢁ ꢁ ꢁF(12) 3.159(2),
˚
P(1)ꢁ ꢁ ꢁF(17) 2.911(1) A in 5a, 3.088(3), 3.126(3) and
˚
2.893(3) A for the corresponding distances in 6a. They
are all shorter than the expected sum of the van der
˚
Waals radii for P and F (1.91 and 1.40 A, respectively
[33]). In both structures, the plane formed by the carbon
atoms C(11)–C(16) of the Ar or Ar0 ring is twisted with
respect to the plane of the Pt(1), P(1), C(10) and Cl(11)
Fig. 2. The crystal structure of trans-[Pt(Cl)(ClC@PAr)(PPh3)2] (5a)
with selected atoms labelled. Displacement ellipsoids for the non-
hydrogen atoms are drawn at the 50% probability level.

S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
3635
atoms, with interplanar angles of 63.02(4)ꢁ in 5a and
66.35(9)ꢁ in 6a, in order to minimise steric interactions.
b.p. 57 ꢁC (0.02 Torr). 31P NMR (CDCl3): d 207.6 (sep-
tet, 4JP–F 20.7 Hz); 19F NMR (CDCl3): d ꢀ59.6 (d, 4JP–F
21.1 Hz, 6F, o-CF3) ppm.
3. Experimental
3.3. Synthesis of [PtCl(ClC@PAr)(PPh3)2] (5a/5b)
All manipulations, including NMR sample prepara-
tion, were carried out under an inert atmosphere of
dry nitrogen or in vacuo, using standard Schlenk proce-
dures or a glovebox. All solvents employed were reagent
grade and dried by refluxing under appropriate drying
agents.
The 31P NMR spectra of phosphorus-containing
starting materials were checked to confirm the absence
of any major impurities. 19F NMR spectra were
recorded on a Varian Mercury 200, Varian VXR 400
or Varian Inova 500 Fourier transform spectrometer
at 188.18, 376.35 and 470.26 MHz, respectively. 31P
NMR spectra were recorded on the same instruments
at 80.96, 161.91 or 202.32 MHz. Chemical shifts were
measured relative to external CFCl3 (19F) or 85%
H3PO4 (31P), with the higher frequency direction taken
as positive. Elemental analyses were performed by the
Microanalytical Services of the Chemistry Department,
University of Durham.
A solution of ArP@CCl2 (0.24 g, 0.6 mmol) in tolu-
ene was added to a solution of Pt(PPh3)4 (0.75 g, 0.6
mmol) in toluene. The resulting yellow solution was al-
lowed to stir. A sample was removed for NMR spectros-
copy. 31P NMR (C7D8): cis-[PtCl(CCl@PAr)(PPh3)2]
2
(5b): d 198.1 (multiplet with Pt satellites, JPt–P 376
Hz, 3JP–P 45.4, 4JP–F 24.4 Hz), 17.3 (dd with Pt satellites,
3
2
1JPt–P 1897, JP–P 46.5, JP–P 16.8 Hz), 14.1 (t with Pt
satellites, 1JPt–P 4064, 3JP–P 15.3 Hz); trans-
[PtCl(CCl@PAr)(PPh3)2] (5a): d 203.7 (multiplet with
2
4
Pt satellites, JPt–P 512, JP–F 22.6 Hz), 24.1 (d with Pt
1
3
satellites, JPt–P 2963, JP–P 29.0 Hz) ppm; 19F NMR
(CDCl3): cis-[PtCl(CCl@PAr)(PPh3)2] (5b): d ꢀ57.9 (d,
4JP–F 23.7 Hz, 6F, o-CF3), ꢀ63.0 (s, p-CF3) ppm;
4
trans-[PtCl(CCl@PAr)(PPh3)2] (5a): d ꢀ58.3 (d, JP–F
23.0 Hz, 6F, o-CF3), ꢀ63.7 (s, p-CF3) ppm. The solution
turned dark orange and an orange precipitate was
formed. This was separated (0.3 g, 0.26 mmol, 43%)
and recrystallised from toluene, to give the trans-
complex 5a (Anal. Found: C, 52.78; H, 3.36%;
Compounds Pt(PPh3)4 [34], ArPCl2 [12,21],
ArP(Cl)CHCl2 (1) [27], ArP@CCl2 (3) [27] and
Ar0PCl2/Ar00PCl2 [19,20] were prepared according to
the literature procedures. ArP(Cl)CHCl2 was synthes-
ised via the direct reaction of CHCl2Li with ArPCl2 at
ꢀ130 ꢁC, rather than via the CdCl2 route [27].
C
49.5H36Cl2F9P3Pt requires C, 51.22; H, 3.13%;
C53H40Cl2F9P3Pt, i.e., with one toluene molecule per
molecule of complex, requires C, 52.75; H, 3.34%).
3.4. Synthesis of [PtCl(CCl@PAr0)(PPh3)2] (6a/6b)
3.1. Synthesis of Ar0P(Cl)CHCl2 (2)
A solution of Ar0P@CCl2 (0.51 g, 1.6 mmol) in ben-
zene was added to a solution of Pt(PPh3)4 (1.9 g, 1.5
mmol). The resulting yellow solution was left to stir,
and a sample was removed for NMR spectroscopy.
31P NMR (C7D8): cis-[PtCl(CCl@PAr0)(PPh3)2] (6b): d
BuLi (15.6 ml, 25 mmol, 1.6 M in hexanes) was added
dropwise to a solution of CH2Cl2 (1.6 ml, 25 mmol) in a
4:1:1 mixture of pentane:THF:Et2O at ꢀ130 ꢁC with
vigorous stirring. The mixture was allowed to stir for 1
h and was then added rapidly through a pre-cooled can-
nula to a solution of Ar0PCl2/Ar00PCl2 (6 g, 20 mmol) in
diethyl ether at ꢀ130 ꢁC. The solution was allowed to
warm up and stirred for 4 h. A precipitate of LiCl
formed. The solution was filtered and the solvent re-
moved under vacuum. The product was purified by dis-
tillation under reduced pressure, giving a colourless oil,
b.p. 65 ꢁC (0.03 Torr). 31P NMR (CDCl3): d 65.3 (septet,
4JP–F 48.8 Hz) ppm; 19F NMR (CDCl3): d ꢀ53.9 (d,
4JP–F 48.9 Hz, 6F, o-CF3) ppm.
2
3
202.4 (septet with Pt satellites, JPt–P 412, JP–P 46.1,
1
4JP–F 22.3 Hz), 17.1 (dd with Pt satellites, JPt–P 1935,
3
3JP–P 46.6, JP–P 16.7 Hz), 13.5 (t with Pt satellites,
1JPt–P 4118, 3JP–P 18.7 Hz); trans-[PtCl(CCl@
2
PAr0)(PPh3)2] (6a): d 208.6 (m with Pt satellites, JPt–P
507, JP–F 24.1 Hz), 24.3 (d with Pt satellites, JPt–P
4
1
3
2992, JP–P 29.8 Hz) ppm; 19F NMR (CDCl3): cis-
4
[PtCl(CCl@PAr0)(PPh3)2] (6b): d ꢀ57.5 (d, JP–F 23.0
Hz, 6F, o-CF3) ppm; trans-[PtCl(CCl@PAr0)(PPh3)2]
4
(6a): d ꢀ58.0 (d, JP–F 23.7 Hz, 6F, o-CF3) ppm. The
solution turned dark orange and an orange precipitate
was formed. The product was isolated (1.2 g, 1.1 mmol,
73%) and recrystallised from toluene to yield the trans-
isomer 6a.
3.2. Synthesis of Ar0P@CCl2 (4)
DBU (2.85 g, 2.8 ml, 18.8 mmol) was added dropwise
to a solution of ArP(Cl)CHCl2 (6.8 g, 18 mmol) in THF.
The solution was stirred for 2 h, giving an orange solu-
tion. The solvent was removed under vacuum and the
product purified by distillation under reduced pressure,
3.5. X-ray crystallography
Single crystal structure determinations were carried
out from data collected using graphite monochromated

3636
S.M. Cornet et al. / Journal of Organometallic Chemistry 690 (2005) 3630–3637
Table 5
Crystal data and structure refinement parameters for 5a and 6a
5a
6a
Empirical formula
Formula weight
Crystal system
C46H32Cl2F9P3Pt, 0.5(C7H8)
1160.68
Triclinic
C45H33Cl2F6P3Pt, 0.5(CH2Cl2)
1089.08
Triclinic
ꢀ
ꢀ
Space group
Crystal size (mm)
Unit cell dimensions
P1
P1
0.30 · 0.30 · 0.30
0.40 · 0.20 · 0.20
˚
a (A)
9.3490(2)
11.6028(2)
9.471(2)
11.653(2)
˚
b (A)
˚
c (A)
22.6978(4)
88.8750(10)
21.394(4)
75.24(3)
a (ꢁ)
b (ꢁ)
c (ꢁ)
83.8450(10)
75.3280(10)
2368.05(8)
91.85(3)
74.64(3)
2189.0(8)
˚
Volume (A)
Z
Temperature (K)
2
120
2
150
Density (g cmꢀ3
)
1.628
3.247
1.652
3.556
l (mmꢀ1
)
Data/restraints/parameters
Rint
14436/0/560
0.0205
11486/1/533
0.0288
R indices [I > 2r(I)]
R indices (all data)
Goodness-of-fit (S)
Residual electron density
R1 = 0.0218, wR2 = 0.0529
R1 = 0.0250, wR2 = 0.0538
1.040
R1 = 0.0397, wR2 = 0.0726
R1 = 0.0658, wR2 = 0.0791
0.916
Dqmax = +1.21, Dqmin = ꢀ0.64
Dqmax = 1.80, Dqmin = ꢀ1.48
˚
Mo Ka radiation (k = 0.71073 A) on a Bruker SMART-
CCD 1K diffractometer. The data were recorded at 120
and 150 K for 5a and 6a, respectively, and the tempera-
ture was controlled using a Cryostream N2 flow cooling
device [35]. In each case, series of narrow x-scans (0.3ꢁ)
were performed at several u-settings in such a way as to
cover a sphere of data to a maximum resolution of 0.70
Appendix A. Supplementary data
Supplementary data associated with this article can
be found, in the online version at doi:10.1016/
j.jorganchem.2005.04.029.
˚
A. Cell parameters were determined and refined using
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