On the products obtained from reaction of rac-diphenyl[2.2] paracyclophanylphosphine with (cycloocta-1,5-diene)palladium(II)chloride

Article abstract of DOI:10.1016/S0020-1693(03)00464-X

The reaction of Pd(cod)Cl₂ (cod=cycloocta-1,5-diene) with 1 and 2 equiv. of rac-diphenyl[2.2]paracyclophanylphosphine, rac-PPh ₂(C₁₆H₁₅), affords the dimer [Pd{PPh ₂(C₁₆H₁₅)}Cl₂]₂ (1) and the square-planar complex trans-Pd{PPh₂(C₁₆H ₁₅)}₂Cl₂ (2), respectively. In solution the dimer undergoes a fluxional process which has been probed by NMR and involves isomerisation between pseudo-trans- and cis-conformations. The structures of trans-[Pd{PPh₂(C₁₆H₁₅)}Cl₂] ₂ (1a) and 2 have been established by single crystal X-ray diffraction; the structure of the dimer is severely disordered. In addition, co-crystals containing both these complexes and solvate molecules have been isolated and their structures established by single crystal X-ray diffraction. The structure of the monomer in the homonuclear and co-crystals are not too dissimilar whereas the structure the dimer has a significantly different structure in the homonuclear and co-crystals. In the homonuclear crystal the central Pd₂Cl₂ unit has a dihedral angle of 26.5° between the two planes whereas the Pd₂Cl₂ unit in the co-crystals is planar.

Full text of DOI:10.1016/S0020-1693(03)00464-X

Inorganica Chimica Acta 354 (2003) 4ꢁ10
/
www.elsevier.com/locate/ica
On the products obtained from reaction of rac-diphenyl[2.2]para-
cyclophanylphosphine with (cycloocta-1,5-
diene)palladium(II)chloride
Damir Blazina a, Simon B. Duckett a, Paul J. Dyson b,*, Rosario Scopelliti b,
Jonathan W. Steed c, Priya Suman d
a Department of Chemistry, The University of York, Heslington, York YO10 5DD, UK
b Institut de Chimie Mole´culaire et Biologique, Ecole Polytechnique Fe´de´rale de Lausanne, CH-1015 Lausanne, Switzerland
c Department of Chemistry, King’s College London, Strand, London WC2R 2LS, UK
d Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK
Received 19 February 2003; accepted 16 June 2003
This paper is dedicated to Prof. Brian F.G. Johnson on the occasion of his 65th birthday
Abstract
The reaction of Pd(cod)Cl2 (codꢀ
/cycloocta-1,5-diene) with 1 and 2 equiv. of rac-diphenyl[2.2]paracyclophanylphosphine, rac-
PPh2(C16H15), affords the dimer [Pd{PPh2(C16H15)}Cl2]2 (1) and the square-planar complex trans-Pd{PPh2(C16H15)}2Cl2 (2),
respectively. In solution the dimer undergoes a fluxional process which has been probed by NMR and involves isomerisation
between pseudo-trans- and cis-conformations. The structures of trans-[Pd{PPh2(C16H15)}Cl2]2 (1a) and 2 have been established by
single crystal X-ray diffraction; the structure of the dimer is severely disordered. In addition, co-crystals containing both these
complexes and solvate molecules have been isolated and their structures established by single crystal X-ray diffraction. The structure
of the monomer in the homonuclear and co-crystals are not too dissimilar whereas the structure the dimer has a significantly
different structure in the homonuclear and co-crystals. In the homonuclear crystal the central Pd2Cl2 unit has a dihedral angle of
26.58 between the two planes whereas the Pd2Cl2 unit in the co-crystals is planar.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Palladium complexes; Phosphine ligands; Co-crystals; X-ray diffraction; Crystal engineering
1. Introduction
complexes have not been widely studied although
several notable papers have been published. For exam-
ple, the crystal structure of Pd{P(CH2OH)3)}4 shows
extensive hydrogen bonding networks between the
Palladiumꢁ
intense research activity largely due to their role as
catalysts in carbonꢁcarbon coupling reactions [1]. Much
effort has been devoted towards deciphering the struc-
ture and bonding in palladiumꢁphosphine complexes as
/
phosphine complexes remain the focus of
/
alcohol functions [3], intermolecular hydrogen
interactions and interactions with the solvate are found
in the crystal structure of cis-Pd(pta)2Cl2 (ptaꢀ1,3,5-
/
Á Á Á
/
metal
/
/
triaza-7-phosphatricyclo[3.3.1.1]decane) [4], and pseudo-
polymeric networks of intermolecular hydrogen bond-
ing interactions involving the ligands and solvate in a
palladium complex with an aminoalcohol functionalised
tertiary phosphine have been reported [5].
Our work on metallocyclophane compounds [6] led to
the preparation of diphenyl[2.2]paracyclophanylpho-
sphine that exhibits a rich coordination chemistry with
palladium(II) and platinum(II)chloride [7] as well as
a greater appreciation of these fundamental properties
should lead to the design of improved catalysts [2].
Intermolecular interactions in palladiumꢁphosphine
/
* Corresponding author. Address: Ecole Polytechnique Fe´de´rale de
Lausanne, Faculte´ des Sciences de Base, Institut de Chimie
Mole´culaire et Biologique, EPFL-BCH, CH-1015 Lausanne,
Switzerland. Tel.: ꢂ
/
41-21-693 9854; fax: ꢂ41-21-693 9885.
/
E-mail address: paul.dyson@epfl.ch (P.J. Dyson).
0020-1693/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00464-X

D. Blazina et al. / Inorganica Chimica Acta 354 (2003) 4ꢁ
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10
5
1
other metals [8]. Some highly unusual structural features
were observed and in this paper we expand on these
earlier investigations.
(NOESY) to fully assign the resonances; the H NMR
data for rac-PPh2(C16H15) are summarised in Table 1.
The reaction of rac-PPh2(C16H15) with 1 equiv. of
(cycloocta-1,5-diene)palladium(II)chloride, Pd(cod)Cl2,
in dichloromethane gives rise to two isomers (see
Scheme 1). The 31P{1H} NMR spectrum of the reaction
solution shows loss of the peak corresponding to the free
phosphine and the generation of two singlet resonances
with relative intensity 3:2 at d 34.58 (major) and 34.18
(minor) in CDCl3 at 296 K. In our previous paper we
assigned these two peaks to two quite different com-
pounds since we obtained a co-crystal containing both a
monomeric and dimeric species [7a]. We have subse-
quently found that these two peaks are actually pro-
duced by isomers of [Pd{PPh2(C16H15)}Cl2]2 (1) that
have pseudo-trans (1a) and -cis (1b) geometries. The 1H
NMR spectrum has been fully assigned using various
2D techniques and full assignments of the spectra for
2. Results and discussion
The bulky phosphine rac-diphenyl[2.2]paracyclopha-
nylphosphine, rac-PPh2(C16H15), is produced in high
yield from the reaction of C16H15Li with PPh2Cl. The
31P{1H} NMR spectrum of rac-PPh2(C16H15) in CDCl3
contains a singlet resonance at d ꢃ/2.43 which is close in
value to that of triphenylphosphine (cf. d ꢃ
/
4.0) [9]. The
1H NMR spectrum of rac-PPh2(C16H15) has not been
reported and is sufficiently complicated to require 2D
NMR experiments involving through bond coupling
networks (COSY) and through space interactions
Table 1
31P and 1H NMR data for the ligand, 1a, 1b and 2 recorded in CDCl3 at 296 K
Ligand
Dimer-1a
Dimer-1b
Monomer 2
Phosphorus-centre
ꢃ/2.43 (s, 1P)
34.58 (s, 1P)
34.18 (s, 1P)
23.00 (s, 1P)
Ph-rings
o-
m-
7.45 (m, 2H)
7.80 (m, 2H)
7.38 (m, 1H)
7.43 (m, 2H)
7.76 (m, 2H)
7.37 (m, 1H)
7.79 (m, 2H)
7.28 (m, 2H)
7.26 (m, 1H)
7.66 (m, 2H)
7.24 (m, 2H)
7.20 (m, 1H)
7.79 (m, 2H)
7.23 (m, 2H)
7.21 (m, 1H)
7.67 (m, 2H)
7.27 (m, 2H)
7.18 (m, 1H)
7.92 (m, 2H)
7.95 (m, 2H)
7.30 (m, 1H)
7.65 (m, 2H)
7.67 (m, 2H)
7.19 (m, 1H)
p-
o-
m-
p-
[2.2]Paracyclophanyl-group
2
6.40 (m, 1H)
5.61 (m, 1H)
6.08 (m, 1H)
6.55 (m, 1H)
6.59 (m, 1H)
6.22 (m, 1H)
6.25 (m, 1H)
2.73 (m, 1H)
2.75 (m, 1H)
2.99 (m, 1H)
2.95 (m, 1H)
3.45 (m, 1H)
3.49 (m, 1H)
2.87 (m, 1H)
2.98 (m, 1H)
6.57 (m, 1H)
6.67 (m, 1H)
6.61 (m, 1H)
6.71 (m, 1H)
8.56 (d, 7.7, 1H)
6.70 (m, 1H)
6.65 (m, 1H)
3.06 (m, 1H)
3.13 (m, 1H)
3.90 (m, 1H)
3.17 (m, 1H)
2.98 (m, 1H)
3.03 (m, 1H)
3.93 (m, 1H)
3.58 (m, 1H)
6.59 (m, 1H)
6.68 (m, 1H)
6.65 (m, 1H)
6.74 (m, 1H)
8.42 (d, 8.2, 1H)
6.73 (m, 1H)
6.66 (m, 1H)
3.10 (m, 1H)
3.19 (m, 1H)
3.59 (m, 1H)
3.22 (m, 1H)
3.53 (m, 1H)
3.96 (m, 1H)
2.89 (m, 1H)
2.94 (m, 1H)
6.52 (m, 1H)
6.95 (m, 1H)
6.90 (t, 6, 6, 1H)
6.38 (d, 8, 1H)
6.72 (m, 1H)
6.68 (dd, 5, 2, 1H)
6.26 (dd, 5, 2, 1H)
3.17 (m, 1H)
2.98 (m, 1H)
2.84 (m, 1H)
2.94 (m, 1H)
3.30 (m, 1H)
3.51 (m, 1H)
3.09 (m, 1H)
3.81 (m, 1H)
4
5
7
8
10
11
13
14
15
16
.

6
D. Blazina et al. / Inorganica Chimica Acta 354 (2003) 4ꢁ10
/
from the stepwise loss of the chlorine and phosphine
1
ligands. The H NMR spectrum has been fully assigned
using 2D techniques and the data are given in Table 1.
2.1. Structural characterisation
Crystals of 1a were grown from CH2Cl2ꢁEt2O by
/
slow evaporation and contain two independent mole-
cules, one of which is shown in Fig. 1 [7b]. Solvate is also
present in the lattice, occupying a cavity in the structure
and not interacting with the palladium complex. The
structure of 1a is severely disordered although the
central Pd2Cl2 core is clearly defined. Each palladium
centre is approximately square-planar, with a dihedral
angle of 26.58 between the two square planes. This type
of distortion is unprecedented in Pd(II) dimers of this
type; the structures of related complexes having planar
structures [12]. In addition, the structure of 1a has also
been determined in co-crystals that also contain 2 (see
below), and in the co-crystals the dimer is planar.
The structure of 2 is shown in Fig. 2 together with
principal bond parameters. Single crystals of 2 were
grown from CH2Cl2ꢁEt2O by slow evaporation and the
/
asymmetric unit contains two half independent mole-
cules (one of which is shown in the figure) and two
dichloromethane solvate molecules. The gross molecular
structure is not too dissimilar to that of the same
molecule observed in the co-crystals (see below) and to
Scheme 1.
both isomers are listed in Table 1. The change in
appearance of the 31P spectrum of 1 revealed that
interconversion occurs between 1a and 1b on the
NMR timescale. This process was monitored in CDCl3
the
related
platinum
complex
trans-
Pt{PPh2(C16H15)}2Cl2 [7c]. The two molecules of 2
differ slightly and it is possible that these differences
can be traced to the way in which the two solvates
interact with them through the formation of weak
hydrogen bonds. The most significant interaction be-
tween the CH2Cl2 solvate and 2 involves a Cl-atom
1
by 1D 31P-EXSY [10] and H lineshape analysis [11].
The rate constant for the conversion of the major to the
minor isomer in CDCl3 at 296 K was found to be 1.19
0.4 sꢃ1, while that for the reverse reaction was 1.89
0.3
ꢃ1, which is in agreement with the observed isomer
/
/
s
ratio (see above). The 1H peak integrations for the
protons in position 8 (see numbering scheme) were used
to obtain K, the equilibrium constant, and the equili-
brium parameters DH8 and DS8 via a Van’t Hoff
analysis over the temperature range 296ꢁ
/
335 K. This
revealed a DH8 of 3.99
/
0.6 kJ molꢃ1 and DS8 of 109
/2 J
Kꢃ1 molꢃ1, which corresponds to a free energy
difference of only 0.9 kJ molꢃ1 at 296 K in CDCl3,
suggesting that there is only a very slight steric interac-
tion between the phosphines in the cis-geometry, while
DH8 reveals that there is essentially no change in the
bond energies between the two isomers of 1.
The reaction of Pd(cod)Cl2 with 2 equiv. of rac-
PPh2(C16H15) in dichloromethane at room temperature
(r.t.) for 1 h affords as trans-Pd{PPh2(C16H15)}2Cl2 (2)
in high yield as shown in Scheme 1. The 31P{1H} NMR
spectrum of 2 contains a singlet resonance at d 23.0. The
mass spectrum of 2 exhibits a molecular ion peak at 963
followed by peaks that correspond to fragment ions
Fig. 1. The molecular structure of [Pd{PPh2(C16H15)}Cl2]2 (1a): key
˚
bond lengths (A) include: Pd(1)Ã
/
P(1) 2.223(2), Pd(1)Ã
/
Cl(1) 2.277(2),
Pd(1)Ã
/
Cl(2) 2.328(2), Pd(1)Ã
/
Cl(3) 2.418(2).

D. Blazina et al. / Inorganica Chimica Acta 354 (2003) 4ꢁ
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10
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we have since found that co-crystallisation of 1a and 2 is
a reproducible phenomenon. Both co-crystals were
grown from dichloromethaneꢁdiethylether solution
/
and one contains CH2Cl2 solvate [7a] molecules and
the other a diethylether solvate [7b]. In the former co-
crystal the CH2Cl2 solvates interact with the complexes
(see Fig. 3) whereas the diethylether in the latter co-
crystal merely occupies a cavity.
The structure of 1a in the co-crystals is markedly
different to that observed in the homonuclear crystal
(see above) whereas the structure of 2 is quite similar.
The structure of the central Pd2Cl2 core in 1a is planar
(it was bent in the homonuclear crystal). Further, in all
the analogues of 1a that have been characterised by X-
ray diffraction the structure is planar rather than bent
[12]. It is not unreasonable to assume that the bent
structure is more strained than the planar structure and
calculations on related systems indicate that this is
indeed the case [16]. It is plausible that the difference
in internal energy between the bent and planar struc-
tures of 1a leads to the formation of the co-crystal. If the
bent structure in homonuclear crystal is of higher
internal energy, then in the presence of other com-
pounds with compatible shapes, in this case 2, co-
crystallisation takes place in preference to the formation
of homonuclear crystallisation. The resulting planar
structure of 1a in the co-crystal is less strained and
therefore of lower energy.
Fig. 2. The molecular structure of trans-Pd{PPh2(C16H15)}2Cl2 (2):
˚
key bond lengths (A) and angles (8) include: Molecule 1; Pd(1)Ã
2.3051(7), Pd(1)ÃP(1) 2.3547(7), Cl(1)ÃPd(1)ÃCl(1)A 180.0, Cl(1)Ã
Pd(1)ÃP(1)A 91.70(3), Cl(1)ÃPd(1)ÃP(1) 88.30(3), C(1)ÃP(1)ÃC(23)
103.36(14), C(1)ÃP(1)ÃC(17) 107.89(14), C(23)ÃP(1)ÃC(17) 98.19(14),
C(1)ÃP(1)ÃPd(1) 111.55(10), C(23)ÃP(1)ÃPd(1) 116.71(10), C(17)Ã
P(1)ÃPd(1) 117.51(10). Molecule 2; Pd(2)ÃCl(2) 2.3061(7), Pd(2)Ã
P(2) 2.3617(7), Cl(2)ÃPd(2)ÃP(2)B 91.67(3), Cl(2)ÃPd(2)ÃP(2)
88.33(3), P(2)BÃPd(2)ÃP(2) 180.0, C(29)ÃP(2)ÃC(51) 107.37(14),
C(29)ÃP(2)ÃC(45) 104.20(14), C(51)ÃP(2)ÃC(45) 96.71(14), C(29)Ã
P(2)ÃPd(2) 114.96(10), C(51)ÃP(2)ÃPd(2) 115.07(10), C(45)ÃP(2)Ã
Pd(2) 116.48(11). and indicate, respectively, the following
symmetry operations: ꢃx, 1ꢃy, ꢃz; ꢃ1ꢃx, ꢃy, 1ꢃz.
/Cl(1)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
A
B
/
/
/
/
/
/
/
Co-crystallisation of substantially different neutral
molecules, excluding solvates, is a rare phenomenon.
coordinated to one of the trans-Pd{PPh2(C16H15)}2Cl2
˚
Cl(1) 2.626 A]. This type of inter-
complexes [H(1s1)/
action is well documented in the literature, with metal-
bound chlorine often accepts hydrogen bonds [13],
Á Á Á
/
although there is still some debate as to whether CÃ
/
H
/
Á Á Á
/
Cl hydrogen bonds are real [14]. However, the
dominant hydrogen bonding interaction in the crystal,
observed in all the related compounds previously
reported [7] involves a direct Pd
/
Á Á Á
/
H interaction with
the formation of a pseudo-octahedral palladium centre
˚
H(10) 2.782 A, Pd(2)
˚
H(42) 2.726 A]. These
[Pd(1)/
Á Á Á
/
/
Á Á Á
/
interactions are very common and transition metal
centres acting as hydrogen bond acceptors has been
described in several papers [15].
Hydrogen bonds to the palladium ions are also
˚
H(42) 2.88
present in 1a [Pd(1)
/
Á Á Á
/
H(14) 2.69 A, Pd(2)
/
Á Á Á
/
˚
A], but in contrast to those is 2, the interaction is only
on one side of the metal centre, thereby forming a
pseudo-square pyramid geometry about the palladiu-
m(II) centre.
2.2. Co-crystals containing 1a and 2
Fig. 3. The molecular structure of the co-crystal containing 1a, 2 and
dichloromethane solvates. The orientation of 1a and 2 in the co-crystal
containing diethyl ether solvate is almost the same and is therefore not
shown. The diethyl ether is disordered and occupies a cavity such that
it does not interact with 1a or 2.
The structure of two co-crystals containing 1a and 2
in a 1:1 ratio have been determined by X-ray diffraction.
Although the discovery of the co-crystal was fortuitous

8
D. Blazina et al. / Inorganica Chimica Acta 354 (2003) 4ꢁ10
/
Key examples include the co-crystallisation of a neutral
mononuclear and dinuclear complexes [17] and poly-
nuclear clusters [18]. Other unusual structural curiosities
3.1.1. Spectroscopic data
31P{1H} NMR (CDCl3) d: ꢃ
2.7 (s). FAB-MS: 392
/
[M]ꢂ. IR (cmꢃ1): (KBr) 2945(s), 1590(s), 1499(s),
1412(s), 1194(s), 1124(s), 1087(s), 1025(w), 935(m),
893(m), 805(m), 743(m), 718(w), 695(w), 621(w), 506(w).
have also been observed for related platinumꢁphos-
/
phine compounds. For example, two different crystals
containing Pt3(m-PPh2)3Ph(PPh3)2 have been analysed
by single crystal X-ray diffraction and shown to have
markedly different trimetal cores [19]. These differences
3.2. Synthesis of [Pd{PPh2(C16H15)}Cl2]2 (1)
were modelled using extended Huckel calculations and
¨
The phosphine rac-PPh2(C16H15) (0.1 g, 0.26 mmol)
and Pd(cod)Cl2 (0.037 g, 0.13 mmol) were stirred in
CH2Cl2 (10 ml) at r.t. for 1 h. The solvent is removed
while somewhat different to the core rearrangements in
the dimers reported herein make an interesting compar-
ison.
under reduced pressure to afford a yellowꢁ
(0.130 g). Crystals were obtained from a solution of
CH2Cl2ꢁEt2O after being left to evaporate at r.t. for
/orange solid
In conclusion, while these structural studies are
unusual, they do not constitute examples of crystal
engineering [20]. However, it is possible that 1a could be
used more generally to induce co-crystallisation based
on the reasoning outlined above. If this is the case then
other molecules that crystallise with structures of
different internal energies could be used in a similar
way in order to engineer co-crystals.
/
several days.
3.2.1. Spectroscopic data for 1
31P{1H} NMR (CDCl3) d: 33.93(s) and 33.53(s).
FAB-MS: 1140 [M]ꢂ, 1105 [Mꢃ
/
Cl]ꢂ, 1068 [Mꢃ
3ClÃ
P]ꢂ, 531 [Mꢃ
P]ꢂ. Analytical data:
%C 55.82, %H 4.36, Calc. 55.91, 4.28 for
Pd2Cl4P2C56H50×CH2Cl2.
/
2Cl]ꢂ, 1031 [Mꢃ
[MꢃClÃPdÃ
P]ꢂ, 570 [Mꢃ
3ClÃPdà 4ClÃPdÃ
P]ꢂ, 497 [Mꢃ
/
3Cl]ꢂ, 639 [Mꢃ
/
/
P]ꢂ, 603
/
/
/
/
2ClÃPdÃ
/
/
/
/
/
/
/
/
3. Experimental
/
All reactions were carried out under an atmosphere of
nitrogen gas using dried and degassed solvents using
Schlenk techniques. [2.2]Paracyclophane was purchased
from Aldrich Chemicals. IR spectra were recorded on a
Mattson research series FTIR instrument. Mass spectra
were recorded using an Autospec FAB instrument
operated in positive mode. NMR spectra were recorded
3.3. Synthesis of trans-Pd{PPh2(C16H15)}2Cl2 (2)
The phosphine rac-PPh2(C16H15) (0.1 g, 0.26 mmol)
and Pd(cod)Cl2 (0.037 g, 0.13 mmol) were stirred in
CH2Cl2 (10 ml) at r.t. for 1 h. The solvent is removed
under reduced pressure to afford a yellowꢁ
(0.130 g). Crystals were obtained from a solution of
CH2Cl2ꢁEt2O after being left to evaporate at r.t. for
/orange solid
1
on a Bruker DRX-400 spectrometer with H at 400.13
/
and 31P at 161.98 MHz, respectively. 1H NMR chemical
shifts are reported in parts per million relative to
residual 1H signals in the deuterated solvent CDCl3
several days.
3.3.1. Spectroscopic data for 2
31P{1H} NMR (CDCl3) d: 22.37(s). FAB-MS: 963
dꢀ
/
7.29, while 31P NMR chemical shifts are reported in
parts per million downfield of an external 85% solution
of phosphoric acid. Standard gradient assisted Hetero-
nuclear Multiple Quantum Correlation (HMQC) [21],
COrrelation SpectrosopY (COSY) [22] and Nuclear
Overhauser Effect SpectroscopY (NOESY) [23] pulse
sequences were used as previously described.
[M]ꢂ, 925 [Mꢃ
/
Cl]ꢂ, 889 [Mꢃ
2ClÃ
/
2Cl]ꢂ, 533 [Mꢃ
/
ClÃ
/
P]ꢂ, 497 [Mꢃ
/
/
P]ꢂ. Analytical data: %C 69.64,
%H 5.12, Calc. 69.90, 5.24 for Pd1Cl2P2C56H50.
3.4. Structural characterisation of 2
3.4.1. Crystal data for 2
C58H54Cl6P2Pd, M 1132.05 g molꢃ1, triclinic, P
/
1;
16.6082(5) A, aꢀ
80.025(1)8, Uꢀ
1.468 Mg mꢃ3, mꢀ
7.77
cmꢃ1, data collected 22031, unique 9381, parameters
608, R1 [F2ꢀ2s(F2)] 0.041, wR2 (all data) 0.106.
˚
˚
3.1. Synthesis of diphenyl[2.2]paracylophanylphosphine,
rac-PPh2(C16H15)
aꢀ
/
12.2649(6) A, bꢀ
82.939(1)8, gꢀ
561.9(2) A , Zꢀ 2, Dcꢀ
/
13.0662(5), cꢀ
/
/
78.983(1)8, bꢀ
/
/
/
2
3
˚
/
/
/
To a solution of C16H15Li (0.74 g, 3.48 mmol) in
diethyl ether (40 ml) at 0 8C, PPh2Cl (0.77 g, 3.48 mmol)
in diethyl ether (20 ml) was added over 10 min. The
reaction was allowed to warm to r.t. and then stirred for
3 h. The solvent was removed in vacuo and the resulting
yellow residue dissolved in hot ethanol. The solvent was
removed under vacuum to give a white solid (0.85 g,
62%).
/
Crystals were mounted using silicon grease on the end
of a glass fibre and cooled on the diffractometer to
100(2) K using an Oxford Cryostream low temperature
attachment. All crystallographic measurements were
carried out with a Nonius KappaCCD diffractometer
equipped with graphite monochromated Mo Ka radia-

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/
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to crystal distance of 25 mm. Integration was carried out
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aid of the program XSEED [26]. All non-hydrogen atoms
were refined anisotropically, whilst hydrogen atoms
were fixed in idealized positions and allowed to ride
on the atom to which they were attached. Hydrogen
atom thermal parameters were tied to those of the atom
to which they were attached. The CIF file for 2 has been
deposited with the Cambridge Crystallographic Data
Centre, CCDC No. 218082. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:
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4. Supplementary material
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1304.
Tables giving crystal data and structure refinement
details, atomic coordinates, thermal parameters, and
bond distances and angles. Ordering information is
given on any current masthead page.
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Acknowledgements
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We would like to thank the Royal Society for a
University Research Fellowship (P.J.D.) and the
EPSRC (P.S.) for financial support. We would also
like to thank Johnson Matthey P.L.C. for the loan of
metal chlorides. The EPSRC and King’s College Lon-
don are also thanked for the provision of the X-ray
diffractometer. The EPFL and Swiss National Science
foundation are also thanked for financial support.
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