Synthesis and reactivity of copper(I) phosphine-alkene complexes: X-ray crystal structure of CuCl(Ph2PCPh=CH2)2

Article abstract of DOI:10.1016/S0277-5387(00)00386-7

Copper(I) chloride complexes containing bifunctional phosphine/alkene ligands of the form CuCl(Ph₂PCH=CH₂)(n) (n = 1, 3) and CuCl(Ph₂PCPh=CH₂)₂ have been synthesized, with the latter being characteriz

Full text of DOI:10.1016/S0277-5387(00)00386-7

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Polyhedron 19 (2000) 1271–1278
Synthesis and reactivity of copper(I) phosphine–alkene complexes:
X-ray crystal structure of CuCl(Ph2PCPh_CH2)2
b
Simon J. Coles a, Paul Faulds b, Michael B. Hursthouse a, David G. Kelly b, , Andrew J. Toner
*
a Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK
b Department of Chemistry and Materials, Manchester Metropolitan University, Chester Street, Manchester, M1 5GD, UK
Received 15 October 1999; accepted 27 March 2000
Abstract
Copper(I) chloride complexes containing bifunctional phosphine/alkene ligands of the form CuCl(Ph2PCH_CH2)n (ns1, 3) and
CuCl(Ph2PCPh_CH2)2 have been synthesized, with the latter being characterized by single crystal X-ray diffraction. Complexes decompose
rapidly on reaction with hydroborating agents NaBH4 and Na[B(OMe)3H], although the thermally unstable Cu(BH4)(Ph2PCPh_CH2)2
may be observed by NMR spectroscopy. The complexes show considerable resistance to thermally initiated alkene polymerization, the only
significant reactivity for diphenylvinylphosphine complexes being trace ligand dissociation and subsequent aerobic oxidation to
Ph2P(O)CH_CH2. Similar dissociation/oxidation is not observed for CuCl(Ph2PCPh_CH2)2. Lewis acid initiated polymerization, using
Et2OPBF3, results in the facile formation of copper(I) coordinated polymeric phosphine ligands for diphenylvinylphosphine complexes, but
again no reactivity is induced in the more sterically hindered a-styrenyl analogue.
q2000 Elsevier Science Ltd All rights reserved.
Keywords: Phosphine; Alkene; Polymerization; Hydroboration; Copper(I) complexes
1. Introduction
conditions are all influential. The reactivityofcopperchloride
systems with triphenylphosphine is illustrative of thisreagent
and condition-based diversity. In addition to [CuCl(PPh3)]4
formed directly from CuCl or by the phosphine reduction
of CuCl2P2H2O [12], CuCl(PPh3)2 or (Ph3P)2CuCl2-
Cu(PPh3)/CuCl(PPh3)3 may be isolated from 1:2
metal:ligand reactions in chloroform and thf, respectively
[13,14]. CuCl(PPh3)3 can also be formed from 1:3 reactions
in a variety of solvents or molten PPh3 [14,15]. Whilst
numerous tertiary phosphine complexes of copper(I) are
reported, the present work focuses on structure and reactivity
in the presence of ancillary alkene functionalities. Thus, as
part of recent investigations of the phosphine/alkene com-
plexes [16,17] we report the synthesis of diphenylvinyl- and
diphenyl-a-styrenyl-phosphine complexes of copper(I),
their potential for thermal and catalysed alkene polymeriza-
tion, and reactivity towards hydroborating agents.
The coordination chemistry of copper has been the subject
of extensive research over several decades [1]. Despite such
thorough activity, the structure and reactivity of copper com-
plexes remains the focus of considerable research effort
[2,3]; copper biochemistry and the stoichiometric use of
organocopper reagents in synthesis are particularly signifi-
cant [4,5]. The stabilization of copper(I) by tertiary phos-
phines forms some of the earliest studies of coordination
chemistry [6,7]. Subsequent work has demonstrated a diver-
sity of structure and stoichiometry derived from the absence
of electronic factors in the d10 electronic configuration. Thus,
whilst monophosphine complexes commonly adopt cubane
or stepped tetrameric solid state structures [8,9], more ster-
ically demanding phosphines can favour the formation of
dimeric and even monomeric complexes [10,11]. The bridg-
ing halide ligands which occur in monophosphine complexes
may be cleaved by the use of greater phosphine:copper(I)
stoichiometries; once again the absence of ligand fieldcontrol
leads to the isolation of numerous products in which the
copper salt, phosphine, reaction solvent and experimental
2. Results and discussion
2.1. Synthesis of complexes
The reaction of copper(I) chloride with 1 equiv. of
Ph2PCH_CH2 in CH2Cl2 affords the monophosphine com-
* Corresponding author. Tel.: q44-161-247-1425; fax: q44-161-247-
6357; e-mail: d.g.kelly@mmu.ac.uk
0277-5387/00/$ - see front matter q2000 Elsevier Science Ltd All rights reserved.
PII S0277-5387(00)00386-7
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plex CuCl(Ph2PCH_CH2) (1), Table 1. Whilst reportsexist
of bidentate diphenylvinylphosphine complexes of silver(I)
[18], IR spectroscopic evidence is indicative of non-bonded
alkene functions in 1. Thus, although 1 has not been struc-
turally characterized, analogy with known complexes sug-
gests the formation of tetrameric solid state species [8]. 1H
NMR spectroscopy is in accord with the presence of pendant
alkene moieties. However, whilst vinylic proton resonances
occur at broadly similar chemical shifts and with similar
couplings to those of free ligand and metal complexed sys-
tems [19], it is notable that the chemical shifts of theterminal
vinyl protons Hb and Hc, Scheme 1, are less separated than
in comparable systems. These resonances are in fact overlaid
and lie at chemical shifts which are reversed relative to their
normal field positions, Table 2. Whilst the assignment of
these overlaid and coupled resonances is readily elucidated
by 1H 2D COSY NMR spectroscopy, Fig. 1, the origin of this
anomalous behaviour is less clear. Since the overlying of Hb
and Hc principally originates from the larger than normal
downfield shift of Hc, it must be speculated that additional
deshielding interactions occur through this moiety. However,
as this effect is not reflected in additional 1H NMR spectro-
Scheme 1. Atom numbering in 1–5.
scopic coupling or shifted 13C{1H} chemicals shifts for the
associated b-carbon, Table 3, it must be consideredasaminor
effect.
The reaction of CuCl and three molar equivalents of
Ph2PCH_CH2 generates the tris-phosphine complex
1
CuCl(Ph2PCH_CH2)3 (2). H, 13C{1H}, 31P{1H} NMR
spectroscopy confirms the conventional P-bound nature of
the phosphine ligands which are spectroscopicallyequivalent
in solution. 1H/13C{1H} 2D COSY NMR spectroscopy, Fig.
2, confirms the assignment of 13C{1H} NMR resonances. 2
precipitates from solution as microcrystalline material cor-
Table 1
Physical and analytical data for complexes 1–4
Complex
Colour
Melting point (8C)
n(C_C) a (cmy1
)
Elemental analysis b
C (%)
H (%)
CuCl(Ph2PCH_CH2) (1)
CuCl(Ph2PCH_CH2)3 c (2)
CuCl(Ph2PCPh_CH2)2 (3)
Ph2P(O)CH_CH2 (4)
white
white
white
white
146
88
145
104
1633
1635
1683
1627
54.0 (54.2)
67.3 (66.6)
71.3 (71.1)
64.7 (64.5)
4.3 (4.1)
6.0 (6.3)
5.3 (5.0)
6.0 (5.7)
a IR, KBr DRIFT reflectance.
b Expected values in parentheses.
c 2P0.5thf.
Table 2
1H NMR (CDCl3) spectroscopic data for complexes 1–5
Complex
Position
Shift (d)
Multiplicity
3Jab (Hz)
3Jac (Hz)
2Jbc (Hz)
nJPH (Hz)
CuCl(Ph2PCH_CH2) (1)
Ph
Ha
Hb
Hc
Ph
Ha
Hb
Hc
Ph
Hb
Hc
Ph
Ha
Hb
Hc
Ph
Hb
Hc
7.34–7.56
6.49
5.96
6.01
7.14–7.52
6.33
5.84
5.60
7.12–7.73
6.09
5.32
7.20–7.55
6.68
6.31
6.27
7.18–7.84
6.25
m
ddd
dd
dd
m
ddd
dd
dd
m
d
d
m
ddd
ddd
ddd
m
dd
dd
11.4
11.4
12.5
12.5
17.8
17.8
18.0
40.7
26.0
0.0
0.0
CuCl(Ph2PCH_CH2)3 (2)
11.7
11.7
20.3
34.4
17.8
0.0
0.0
CuCl(Ph2PCPh_CH2)2 (3)
Ph2P(O)CH_CH2 (4)
0.0
0.0
24.9
11.7
12.5
12.5
18.7
18.7
24.5
41.0
22.3
1.8
1.8
Ph2P(O)CPh_CH2 (5)
1.1
1.1
40.3
19.4
5.76
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Fig. 1. 1H 2D COSY NMR spectrum of CuCl(Ph2PCH_CH2) (1) in CDCl3 showing coupling of vinylic protons.
Table 3
31P{1H} and 13C{1H} NMR spectroscopic data for complexes 1–5
Complex
31P{1H} a (d)
13C{1H} b (d)
a
b
i
o
m
p
CuCl(Ph2PCH_CH2) (1)
CuCl(Ph2PCH_CH2)3 (2)
CuCl(Ph2PCPh_CH2)2 (3)
y5.6 c
y8.6 d
y9.8 c
y11.3 d
0.0 c
132.29
(18.3)
131.97
(20.7)
139.98
(14.7)
131.70
(8.6)
130.40
(8.5)
132.04
(9.8)
133.24
(38.0)
132.80
(27.3)
130.76
(31.8)
130.85
(6.1)
128.96
(9.7)
127.71
(8.5)
128.57
(9.8)
128.34
(s)
133.62
(14.8)
132.94
(13.5)
134.38
(14.6)
127.84
(10.9)
128.97
(12.2)
130.29
(s)
129.99
(s)
130.08
(s)
127.67
(s)
PPh2
y1.2 d
PCPh
Ph2P(O)CH_CH2 (4)
Ph2P(O)CPh_CH2 (5)
23.3 c
18.7 d
19.4 c
16.0 d
131.65
(96.5)
135.04
(s)
132.80
(106.2)
131.75
(9.7)
132.26
(2.5)
a Ph2PCH_CH2, 31P{1H}, CDCl3, dsy11.4; Ph2PCPh_CH2, 31P{1H}, CDCl3, dsy6.8.
b nJ(CP) (Hz) in parentheses, CDCl3.
c CDCl3.
d C7D8.
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Fig. 2. 1H/13C{1H} 2D COSY NMR spectrum of CuCl(Ph2PCH_CH2)3 (2) in CDCl3.
responding to the solvate 2P0.5thf. Evidence for this formu-
lation is provided by 1H NMR spectroscopy which identifies
non-bonded thf at ds1.82 (t) and 3.70 (t) in CDCl3, and
thermogravimetric analysis which yields a mass loss of 4.5%
(4.7%) in the temperature range 50–608C.
proton-coupled 13C NMR spectroscopy result in complex
spectra as a consequence of extensive 2J(CH) and 3J(CH)
1
coupling. H/13C{1H} 2D COSY NMR spectroscopy pro-
vides in simpler route to such interpretation, Fig. 3, from
which 13C{1H} and 13C NMR resonances, as well as nJ(CP)
and nJ(CH) couplings, can be assigned. The latter couplings
are typical of phosphorus(V) interaction with aromatic and
alkene sp2 carbons.
In contrast to the formation of 2, the reaction of CuCl and
3 equiv. of Ph2PCPh_CH2 results in the isolation of
CuCl(Ph2PCPh_CH2)2 (3) on recrystallization from
CH2Cl2/Et2O. The increased cone angle of the a-styrenyl
ligand evidently favours bis-complex formation on steric
grounds. Such changes in stoichiometry from reactant to
product are not unusual, the facile modification of
metal:ligand stoichiometry has been observed in other
copper(I) phosphines, for example the shift from
Cu(NO3)(PPh3)3 to Cu(NO3)(PPh3)2 on recrystallization
[20]. Phenyl substitution in 3 relative to the vinyl complexes
1 and 2 results in a significant simplification of the 1H NMR
features associated with the alkene moiety, with protons cen-
tred at the b-carbon being reduced to phosphorus-coupled
doublets, Table 2.
Since phosphineoxidationformsafaciledeactivationpath-
way for both phosphine ligands and complexes at ambient or
elevated temperatures [21,22], the phosphine oxides
Ph2P(O)CH_CH2 (4) and Ph2P(O)CPh_CH2 (5) have
been prepared by peroxydisulfate oxidation of the corre-
sponding phosphines. Analytical and spectroscopic data
again confirm the integrity of these products, Tables 1–3.
Attempts to assign the 13C{1H} NMR resonances of 4 using
2.2. Thermal and Lewis acid catalysed polymerization
studies
The thermal effects of heating complexes 1–3 to 1008C in
deuterated toluene have been followed using 31P{1H} NMR
spectroscopy. In inert atmospheres no evidence for chemical
change can be observed for 1–3 over 8 h. Under similar
conditions in air, 1 and 2 show trace oxidation (-5%) to
free 4 (31P{1H} C7D8 ds18.7), although no loss of integrity
is recorded for the more sterically hindered a-styrenyl com-
plex 3. Since vinyl and a-styrenyl substituted phosphine
ligands are readily distinguish from their saturated or poly-
merized analogues in 31P{1H} NMR spectroscopy by the
respective presence and absence of diamagnetic deshielding
[16], it is evident that these complexes display no propensity
for thermally initiated alkene polymerization.
Early reports have demonstrated that both free
Ph2PCH_CH2 [23] and its silver(I) complexes [18]
undergo Lewis acid catalysed alkene polymerization. Thus,
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1275
Fig. 3. 1H/13C{1H} 2D COSY NMR spectrum of Ph2P(O)CH_CH2 (4) in CDCl3.
Et2OPBF3 catalysed polymerization studies have been per-
formed in CDCl3 and followed using NMR spectroscopy.
The exposure of 1 to Et2OPBF3 over ca. 1 h results in the
precipitation of [CuCl(Ph2PCH–CH2–)n] (6) (C 54.0
(54.3); H 4.2 (4.2)) in ca. 80% yield. The corresponding
reaction of 2 affords precipitates of variable hydrocarbon
content consistent with concomitant ligand polymerization
and dissociation. Since [CuCl(Ph2PCH–CH2–)n] (6) (and
its corresponding product obtained from 2) are insoluble in
common NMR solvents, spectroscopic evidence to support
polymerization is limited. No IR band corresponding to
n(C_C) can be located, however, such absorbancesareoften
weak and difficult to assign even in authentic diphenylvinyl-
phosphines. Thus interpretation is limited to elemental anal-
ysis consistent with the formation of 6. Whilst it is obvious
that 2 would provide identical elemental analysis, the consid-
erable solubility of 2, Et2OPBF3 and the common decompo-
sition product 4, in CDCl3 preclude the presence of these
materials. The composition of the remainingreactionsolution
material is complex and dynamic. 31P{1H} NMR spectros-
copy identifies five principal components, although their rel-
ative proportions vary with time and decrease overall relative
to numerous other species. After 1 day a copper(I)phosphine
complex (dsy5.4 and 2.5 ppm), the [Ph2PCH_CH2PBF3]
adduct (ds1.7 ppm) and additional products ds17.1 ppm
(dd Js62.5 and 1187.6 Hz) and ds22.3 ppm (dd Js58.9
and 183.9 Hz) are all observed. The propensity for rapid
phosphine exchange, plus the complex vinylic and ethylene
resonances present in 1H NMR spectra, make detailed inter-
pretation impossible. However, furtherBF3 reactivitybeyond
simple Lewis acid behaviour is certainly possible. Fluoride
and tetrafluoroborate complexes of copper(I) phosphinesare
known [24], whilst the formation of BF4y complexes from
the reaction of Et2OPBF3 and PdCl2P2 complexes is well
established [25].
CuCl(Ph2PCPh_CH2)2 (3) is inert under the conditions
which produce reactivity in 1 and 2; 3 is recoveredunchanged
from exposure to Et2OPBF3. In view of the ease with which
styrene undergoes thermal and catalysed polymerization rel-
ative to ethene, the greater stability of 3 is notable. Since
neither structural nor spectroscopic characterization of 3 sug-
gests anomalous behaviourcomparedto1, 2orCuCl(PPh3)n,
it must be suggested that coordination to the relatively
crowded CuClP2 centre and the presence of the a-phenyl
moiety are sufficient to inhibit reactivity.
2.3. Reactivity of copper complexes towards hydroborating
agents
Although Cu(BH4) decomposes below ambient tempera-
ture, in the presence of tertiary phosphine and/or phenan-
throline ligands, NaBH4 reacts with copper(I) salts to form
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stabilized complexes. The system is particularly sensitive to
the nature of the phosphine employed with only triarylphos-
phines, PPh2Me and various chelating phosphines containing
PPh2 fragments affording products with extended lifetimes
at, or above, ambient temperature [26]. Since initial reports
in this area, several strands of activity have been pursued,
focusing on both structure and reactivity. Interest centres on
the relationship between stoichiometry and tetrahydroborate
bonding [27], and on the application of transition metal
tetrahydroborates to regioselective reduction [28]. Substi-
tuted tetrahydroborates have allowed further modification
of reduction reactivity, and have afforded the stable hexa-
meric hydride [CuH(PPh3)]6 from the reaction of
Na[B(OMe)3H] and CuCl(PPh3) [29], although the latter
reaction is again critically dependent on the phosphine
present.
Since the range of tertiary phosphines which stabilize cop-
per(I) tetrahydroborates and hydrides is limited, it is inevi-
table that the isolation of Ph2PCH_CH2 and Ph2PCPh_CH2
complexes will be, at best, difficult. Indeed the reaction of 1–
3 and Na[B(OMe)3H] at y108C proceeds through a tran-
sient red intermediate to afford metallic copper and free
Ph2PCH_CH2 or Ph2PCPh_CH2; the coloration of the inter-
mediate is consistent with that of [CuH(PPh3)]6. At lower
temperatures reaction and decomposition progress more
slowly, but there is no evidence for the formation of a kinet-
ically stable hydride. 1 and 2 also form unstable products on
reaction with NaBH4, metallic copper andfreePh2PCH_CH2
being identified. Once again the reactivity of 3 contrasts with
that of 1 and 2. Reaction of 3 with a slight excess of finely
ground NaBH4 in CDCl3 at y108C affords complete con-
version to Cu(BH4)(Ph2PCPh_CH2)2 (7). The long-term
instability of 7 has prevented elemental analysis; however,
NMR is consistent with the formulation presented. 1H NMR
data are clearly indicative of a change of Ph2PCPh_CH2
environment with modifications in both chemical shift and
3J(PH) couplings for Hb and Hc (1H (CDCl3) ds6.16 (d,
3J(PH)s25.7 Hz), 5.38 (d, 3J(PH)s12.6 Hz)), and since
there is no evidence for free phosphine, it is reasonable to
assume the 1:2 copper:phosphine stoichiometry is main-
Fig. 4. Single crystal X-ray diffraction structure of CuCl(Ph2PCPh_CH2)2
(3).
2.4. Single crystal X-ray diffraction characterization of
CuCl(Ph2PCPh_CH2)2 (3)
Whilst numerous copper(I) phosphine complexes have
been crystallographically characterized, the majority of stud-
ieshave focusedonelucidatingtherelationshipbetweencom-
plex structure and phosphine steric/electronic parameters in
[CuClP]n complexes [1]. Structural determinations of
CuClP2 donor sets are less common; only CuCl[P(o-
tolyl)3]2 [31] and two forms of solvated CuCl(PPh3)2
[9,14] have been reported. Thus, suitable crystals of 3,
formed by recrystallization from CH2Cl2/Et2O, were studied
by X-ray diffraction. Structural characterization, Fig. 4, indi-
cates a three coordinate copper(I) structure with P-bound
ligands and pendant styrene moieties. No local symmetry is
observed at the metal centre; however, NMR spectroscopic
evidence consistently demonstrates the equivalence of phos-
phine ligands in solution. Thus, in the absence of ligand field
influences, solid state asymmetry is clearly dependent on
steric and packing factors.
Bond lengths in 3 are broadly similar to those of
CuCl(PPh3)2, Table 4. Bond angles indicate an almostplanar
arrangement around the copper centre. The steric repulsion
of the phosphine ligands is demonstrated by the large P–Cu–
P angle, with considerable asymmetry being apparent from
the two P–Cu–Cl angles. Once again similar features have
been observed in CuCl(PPh3)2, although the deviations from
an idealized trigonal planar geometry are more pronounced
in 3.
y
1
tained. The BH4 moiety is observed in H and 11B{1H}
NMR (1H (CDCl3) ds1.59 (q, 1J(11BH)s24.3 Hz),
11B{1H} (CDCl3) dsy36.5). 31P{1H} NMR spectroscopy
is less informative owing to the facility of copper(I) com-
plexes to undergo rapid ligand exchange, a feature which is
typified by the observation of a single resonance for
Cu(BH4)(PPh2Me)3 and PPh2Me mixtures [28]. In 7 a sin-
gle new 31P{1H} NMR spectroscopic resonance is recorded
at 1.0 ppm. Supporting evidence for the presence of coordi-
nated BH4y is provided by solid state IR spectroscopy, from
which bands at 2381 and 2011 cmy1 are identified. These are
less separated than the terminal and bridging n(Cu–Ht) and
n(Cu–Hb) bands of most pseudo-tetrahedral Cu(h2-BH4)P2
3. Conclusions
Copper(I) forms complexes with diphenylvinyl- and
diphenyl-a-styrenyl-phosphine in which phosphine ligands
adopt P-bound coordination. Pendant alkene moieties are
thermally stable, but vinyl functions polymerize in the pres-
y
systems, but are certainly indicative of BH4 coordination
[30].
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1277
Table 4
o
˚
Selected bond lengths (A) and angles ( ) for CuCl(Ph2PCPh_CH2)2 (3)
b
CuCl(Ph2PCPh_CH2)2 (3)
CuCl(PPh3)2P0.5thf a
CuCl(PPh3)2P0.5C6H6
Cu–Cl
Cu–P(1)
Cu–P(2)
C(13)–C(14)
C(33)–C(34)
2.214(2)
2.224(2)
2.242(2)
1.319(7)
1.344(8)
2.214(1)
2.2564(9)
2.2676(9)
2.208(2)
2.260(2)
2.272(2)
Cl(1)–Cu–P(1)
Cl(1)–Cu–P(2)
P(1)–Cu–P(2)
120.95(6)
109.61(6)
127.93(6)
120.58(4)
113.86(4)
125.55(4)
120.74(6)
113.76(7)
125.48(7)
a Ref. [14].
b Ref. [9].
ence of boron trifluoride. Phenyl substitution of the a-carbon
renders the alkene less susceptible to polymerization, butalso
affords a tetrahydroborate complex that is sufficiently stable
to allow NMR characterization.
4.3. Ligand synthesis
Ph2PCH_CH2 was prepared by the Grignard route from
commercialCH2_CHMgBrandPh2PCl. Ph2PCPh_CH2 was
similarly prepared using Grignard formed by the reaction of
a-bromostyrene and magnesium turnings. Syntheses fol-
lowed conventional procedures [34]. In each case the 1H and
31P{1H} NMR data are comparable with literature values
[35].
4. Experimental
4.1. Single crystal X-ray diffraction
4.4. Complex synthesis
Crystal data for [CuCl(Ph2PCPh_CH2)2] (3),
C40H34ClCuP2. Crystal dimensions 0.05=0.05=0.2 mm.
Ms675.60, monoclinic, space group P21/C. as9.207(2),
Two synthetic routes were utilized, i.e. the stoichiometric
reaction of copper(I) chloride or the reduction of hydrated
copper(II) chloride in the presence of excess phosphine.
Whilst both routes are acceptable, the former is preferable in
termsofyieldandcontrolofmetal:ligandstoichiometry.Thus
the following is typical; 2.00 g copper(I) chloride (2.02
mmol) is slurried in dry dichloromethane (45 cm3). One
equivalent of Ph2PCH_CH2 (ca. 4.5 g, 2.1 mmol) is added
and the reactants stirred until the insoluble salt is consumed.
The solution is then filtered and 1 precipitated by the addition
of hexane. Separation of the resulting solid by filtration and
drying in vacuo affords 1 in 95% yield.
˚
bs9.894(2), cs36.510(7) A, bs93.80(3)8, Vs
3318.5(12) A , Zs4, Dcalcs1.352 g cmy3, Ts293(2) K,
3
˚
l(Mo Ka)s0.71073 nm, m(Mo Ka)s0.863 mmy1
;
observed data 4748, unique no. of observed data 3115
(I)2s(I)), Rs0.0566, wRs0.1352. Max./min. final dif-
ferenceq0.472/y0.390 eAy3. Intensitydatawererecorded
˚
on a FAST TV area detector following previously described
procedures [32]. The structure was solved by direct methods
(SHELXS-86) and refined by full matrix least squares on F2
(SHELX-92), with all non-hydrogen atoms being refined
anisotropically. Hydrogen atoms were assigned fixed posi-
tions and thermal parameters defined by their respective car-
bon atoms.
4.5. Phosphine oxide synthesis
4.5.1. Ph2P(O)CH_CH2
Ph2PCH_CH2 (1.08 g; 5.1 mmol) was dissolved in
CH2Cl2 (25 cm3) and slurried with Oxonew for 1 day, after
which the solution was filtered and concentrated to dryness
affording Ph2P(O)CH_CH2 in quantitative yield. 1H,
13C{1H} and 31P{1H} NMR: see Tables 2 and 3. IR (KBr):
n(O_P) 1174 cmy1. MS (EI) m/es228 (100%).
Ph2P(O)CPh_CH2: The compound was similarly prepared
and characterizedby1Hand 31P{1H} NMRspectroscopy(see
Table 3). IR (KBr): n(O_P) 1189 cmy1. MS (EI) m/
es305 (100%).
4.2. Spectroscopy
All reactions were carried out under nitrogen using dry
degassed solvents using previously described methods [33].
1H, 13C{1H}, 13C and 31P{1H} NMR spectra were obtained
at 270.05, 67.8 and 81.1 MHz, respectively, in CDCl3 and/
or C7D8, on a JEOL GSX-270 instrument. Standard acquisi-
tion parameters were used in each case, although 8–10 s pulse
delays were found necessary to obtain reasonable 13C{1H}
and 13C NMR spectra. 1H/13C{1H} 2D COSY NMR spectra
were obtained using the pulse sequence (p/2, 1H)–(t1/2)–
4.6. Thermal polymerization studies
D1–(p/2, 1H; p/2, 13C)–D2, where D1s /2J and D2s /4J
and Js120 Hz [19].
The following is typical: 1 (4.3 mg) was dissolved in dry
degassed C7D8 (2.0 cm3) and placed in a sealed 4.0 mm
1
1
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1278
S.J. Coles et al. / Polyhedron 19 (2000) 1271–1278
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NMR tube under nitrogen. The solution was heated to 1008C
for periods of 1 h for up to 8 h. After each hour the tube was
cooled to ambient temperature and the NMR spectrum
recorded.
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57–60.
4.7. BF3 initiated polymerization studies
An NMR sample of 1 (6.3 mg) was prepared in CDCl3 as
above and Et2OPBF3 (10 ml) added under nitrogen. The
NMR spectrum was obtained after 1 h, 1 day and 7 days at
ambient temperature, precipitated material being removedby
filtration and dried in vacuo. Additional CDCl3 was added to
the remaining solution to maintain constant volume.
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4.8. Reactions with NaBH4 and NaB(OMe)3H
NaBH4 (5.0 mg; 0.13 mmol) was placed in a dry 4.0 mm
NMR tube under nitrogen and cooled to y108C. A solution
of 1 (23.3 mg; 0.11 mmol) was prepared in CDCl3 (2.0
cm3), precooled to y108C and transferred to the NMR tube
under nitrogen. NMR spectra were obtained after 1 h and
1 day.
Supplementary data
[20] F.H. Jardine, A.G. Vohra, F.J. Young, J. Inorg. Nucl. Chem. 33
(1971) 2941.
[21] S.M. Godfrey, D.G. Kelly, C.A. McAuliffe, R.G. Pritchard, J. Chem.
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Crystallographic data for structural analysis have been
deposited with the Cambridge Crystallographic Data Centre,
CCDC No. 134113. Copies of this information may be
obtained free of charge from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: q44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
[26] T.J. Marks, J.R. Kolb, Chem. Rev. 77 (1977) 263 and Refs. therein.
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Acknowledgements
[29] M.R. Churchill, J.M. Wormald, J. Am. Chem. Soc. 93 (1971) 2063.
[30] F. Cariati, L. Naldini, Gazz. Chim. Ital. 95 (1965) 3.
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Papasergio, A.H. White, Inorg. Chem. 26 (1987) 3533.
[32] J.A. Darr, S.R. Drake, M.B. Hursthouse, K.M.A. Malik, Inorg. Chem.
32 (1993) 5704.
Mr P. Warren is thanked for his help and advice in obtain-
ing NMR data. PF and AT acknowledge the award of HEFC
and MMU Faculty funded studentships.
[33] S.J. Coles, M.B. Hursthouse, D.G. Kelly, G.C. Ranger, A.J. Toner,
N.M. Walker, J. Organomet. Chem. 580 (1999) 304.
[34] V.D. Biano, S. Doronzo, Inorg. Synth. 16 (1976) 155.
[35] L. Maier, in: L. Maier, G.M. Kosolapoff (Eds.), Organic Phosphorus
Compounds, vol. 1, Wiley-Interscience, New York, 1972, Ch. 1 and
Refs. therein.
References
[1] B.J. Hathaway, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty
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Oxford, 1987, Ch. 53.
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