Reactions of a phosphavinyl Grignard reagent with main group mono-halide compounds

Article abstract of DOI:10.1016/S0022-328X(02)02104-6

The reactions of a phosphavinyl Grignard reagent, [CyP=C(Bu^t)MgCl(OEt₂)] Cy=cyclohexyl, with a variety of main group 13, 14 and 16 mono-halide compounds have been investigated. When the Grignard reagent is reacted with bromocatecholb

Full text of DOI:10.1016/S0022-328X(02)02104-6

Journal of Organometallic Chemistry 665 (2003) 127Á134
/
www.elsevier.com/locate/jorganchem
Reactions of a phosphavinyl Grignard reagent with main group
mono-halide compounds
Simon Aldridge a, Cameron Jones a,*, Peter C. Junk b, Anne F. Richards a,
Mark Waugh a
a Department of Chemistry, University of Wales, Cardiff, P.O. Box 912, Park Place, Cardiff CF10 3TB, UK
b School of Chemistry, Box 23, Monash University, Clayton, Vic., 3800, Australia
Received 18 September 2002; received in revised form 1 November 2002; accepted 1 November 2002
Abstract
The reactions of a phosphavinyl Grignard reagent, [CyPÄ
14 and 16 mono-halide compounds have been investigated. When the Grignard reagent is reacted with bromocatecholborane the
terminal phosphavinyl complex, [(C6H4O2)B{C(But)Ä
PCy}], is formed. Related terminal phosphavinyl tin and gallium complexes,
[R3Sn{C(But)Ä Me or Bun and [IGa{C(But )Ä
PCy}], Rꢀ PCy}2], have been prepared by similar routes. The reaction of the
Grignard reagent with PhSeCl has afforded a new l5,l5-diphosphete, [{(But)CP(Cy)(SePh)}2], the mechanism of formation of which
is discussed. The preparation of a phosphavinyl selenium compound, [(C8H4O2N)PÄ
C(But)(SePh)], is also described. All
/
C(But)MgCl(OEt2)] Cyꢀ
/cyclohexyl, with a variety of main group 13,
/
/
/
/
/
compounds have been spectroscopically characterised and several have been crystallographically authenticated.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Phosphavinyl; Grignard; Main group; Low coordination; Phosphorus
1. Introduction
great interest in their own right the preparation of
stable, terminal phosphavinyl-main group complexes
would allow an entry into their use as reagents in
synthetic techniques such as Stille type coupling reac-
tions. It was apparent that the reaction of phosphavinyl
Grignard reagents with main group monohalide com-
In recent years we have been systematically investi-
gating the reactivity of phosphavinyl Grignard reagents,
[RPÄ
/
C(But)MgCl], Rꢀ
/
alkyl or aryl [1], toward main
group [2Á
/
4] and transition metal [5,6] halide complexes.
Our original aim was to prepare terminal phosphavinyl
metal complexes, which it was believed would prove
useful as reagents in organophosphorus and phospha-
organometallic synthesis, especially considering the wide
pounds, RnEX, Rꢀ
could afford such stable compounds, e.g. RnEÃ
PR, which are exempt from intramolecular phosphavi-
nyl coupling reactions. Our efforts in this area are
reported herein.
/
alkyl, aryl etc., Xꢀ
/
halide, nꢀ
/
0Á3,
/
/
C(But)Ä
/
applicability of vinylÁmetal complexes in synthesis [7].
/
However, we have found that, although relatively stable
terminal phosphavinyl complexes can be formed, e.g.
[Me2Sn{C(But)Ä
/
PCy}2] (1) [2] and [CyIn{C(But)Ä
cyclohexyl [3], metal mediated phos-
/
PCy}2] (2) Cyꢀ
/
phavinyl coupling reactions more commonly occur to
give unusual heterocyclic or metallocage compounds,
e.g. 3 [4] and 4 [3]. Although these compounds are of
* Corresponding author. Tel.: ꢁ
874030
E-mail address: jonesca6@cardiff.ac.uk (C. Jones).
/
44-29-20-874060; fax: ꢁ44-29-20-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 1 0 4 - 6

128
S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á134
/
2. Results and discussion
of this work the 1:1 reaction of 5 with ‘GaI’ was
attempted. This reagent is formed via the sonication of
gallium metal and half an equivalent of I2 in toluene
[11], though its actual composition is not yet known.
When the reaction with 5 was carried out, gallium metal
deposition was observed and the 31P-NMR spectrum of
the reaction mixture showed only a low field resonance
at 307.2 ppm, in the normal region for phosphavinyl
fragments [12]. In contrast to the corresponding Tl and
In reactions, there was no formation of the coupled
product, Cy2P2C2But2. Recrystallisation of the reaction
mixture afforded a moderate yield of the Ga(III)
compound, 7, (Scheme 1). It seems that this probably
The use of vinyl boronic acids and esters in transition
metal catalysed CÃ/C bond forming reactions, e.g.
Suzuki cross couplings, is well established [8]. It seemed
logical that if the phosphavinyl equivalents of these
reagents could be prepared they may prove useful in
organophosphorus synthesis. To this end bromocate-
cholborane was treated with one equivalent of [CyPÄ
/
C(But)MgCl] (5) which led cleanly to a moderate yield
(65%) of the waxy solid, 6, after extraction of the
reaction mixture with hexane (Scheme 1). Although
NMR spectroscopy showed the material to be of high
forms via an intermediate, [GaI{C(But)Ä
/PCy}], which
purity (ꢀ95%) it could be obtained analytically pure,
/
though in lower yield (30%), by sublimation. The NMR
spectroscopic data for the compound were as expected
and most notably the 31P-NMR spectrum exhibited a
singlet at low field, 322.3 ppm, very close to that for 5
(324 ppm). An inspection of the 11B-NMR spectrum of
6 revealed a singlet resonance at 31.5 ppm, which is
consistent with the presence of the catecholboryl moeity.
Thallium(I) and indium(I) alkyls have found signifi-
cant use as alkyl transfer reagents in organometallic
synthesis [9]. Therefore, it seemed worthy to attempt the
reacts with ‘GaI’ in a series of redistribution and
disproportionation reactions to give 7 and two equiva-
lents of gallium metal. The reaction occurred too rapidly
for the proposed intermediate to be observed by 31P-
NMR spectroscopy.
Although 7 is closely related to 2, its chloro analogue,
[ClGa{C(But)Ä
/
PCy}2], has been proposed as a short
lived intermediate in the formation of 4 from GaCl3 and
three equivalents of 5 [3]. In that work it was believed
that [ClGa{C(But)Ä
/PCy}2] underwent a rapid phospha-
preparation of [M{C(But)Ä
/
PCy}], Mꢀ/Tl or In, via the
vinyl coupling reaction and substitution of the chloride
ligand with a third equivalent of 5 to give 4. Interest-
ingly, if 7 is treated with one equivalent of 5 no reaction
occurs. It is not known why varying the nature of the
halide ligands in 7 would have such a significant impact
on its reactivity.
reaction of 5 with MCl. In both reactions, however,
metal deposition was observed and high yield forma-
tions of the known 2,4-diphosphabicyclobutane, Cy2-
P2C2But2, occurred, presumably as a result of an
oxidative coupling of two phosphavinyl fragments. It
is noteworthy that we have observed similar couplings in
the reaction of 5 with PbCl2 which also lead to
deposition of the metal involved [10]. As an extension
The molecular structure of 7 is depicted in Fig. 1
(Table 1). It is monomeric and as with the closely related
compound, 2, the metal centre has a trigonal-planar
Scheme 1.

S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á
/134
129
˚
Fig. 1. Molecular structure of 7. Selected bond lengths (A) and angles (8): I(1)Ã
C(1) 1.674(2), P(2)ÃC(12) 1.671(2), C(12)ÃGa(1)ÃC(1) 130.77(9), C(12)ÃGa(1)Ã
121.17(13), P(2)ÃC(12)ÃGa(1) 122.00(13).
/
Ga(1) 2.5364(7), Ga(1)Ã
/
C(12) 1.968(2), Ga(1)Ã
Ga(1)ÃI(1) 114.98(7), P(1)Ã
/
C(1) 1.973(2), P(1)Ã
/
/
/
/
/
/
I(1) 114.22(6), C(1)Ã
/
/
/
C(1)ÃGa(1)
/
/
/
2
coordination environment (S anglesꢀ
the phosphavinyl fragments have retained their Z-
stereochemistry and the two unsaturated PÃC bond
lengths (1.672 A avge.) are in the normal region for
localised double bonds [12]. All other bond lengths and
angles within the compound are unexceptional.
/
359.978). Both
lites with JSnP couplings in the expected region (8 d
325.2 ppm, 2JSnP 157 Hz; 9 d 324.8 ppm, 2JSnP 144 Hz).
The magnitude of these couplings were also reflected in
the 119Sn spectra of 8 and 9 which exhibited doublet
/
˚
resonances centred at ꢂ
/
60.3 and ꢂ54.2 ppm, respec-
/
tively.
The Stille cross coupling of vinyl-trialkyltin com-
pounds with organic electrophiles in the presence of a
transition metal catalyst is a powerful synthetic tool,
widely utilised by organic chemists [13]. The preparation
of the phosphavinyl analogues of these tin reagents
could lead to their use as building blocks in the synthesis
of new mono- and multi-dentate phosphorus based
ligand systems using Stille methodology. The formation
of these tin reagents seemed feasible given our previous
preparation of the related bis-phosphavinyl tin complex,
1 [2]. This was readily achieved by reacting one
equivalent of 5 with trialkyl tin chlorides to give the
products, 8 and 9, in high yields (Scheme 1). Both
compounds are liquids at room temperature and can be
obtained simply by filtering the reaction mixtures and
removing the solvent from the filtrate in vacuo. The
purity of these crude products was found by NMR
spectroscopy to be greater than 98% and thus no further
purification was attempted. Their 31P-NMR spectra
both displayed low field singlets having 117,119Sn satel-
Vinyl selenide compounds are useful reagents in
hetero-organic synthesis [14]. Again it would be valuable
to prepare the phosphavinyl analogues of these com-
pounds and explore their utility in organic transforma-
tions. We have previously achieved this by the 1,2-
additions of phenylselenyl halides to phosphaalkynes,
PÅ
/
CR, Rꢀ
But, adamantyl. However, although these
/
additions were high yielding they were not stereo- or
regiospecific, and thus of limited value [15]. The reaction
of phenyl selenyl halides with 5 could potentially over-
come this problem and lead, stereospecifically, to the Z-
phosphavinyl complex, Z-[PhSe{C(But)Ä
/
PCy}]. In
practice, however, a very different result occurred. The
1:1 reaction of PhSeCl with 5 in diethyl ether afforded a
high yield of the 1,3-l5,l5-diphosphete, 10, after recrys-
tallisation from hexane (Scheme 1). When this reaction
was monitored by 31P-NMR spectroscopy a singlet was
initially observed at 320 ppm which upon warming to
room temperature rapidly diminished and a new singlet
appeared at 45.2 ppm which possesses 77Se satellites

130
S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á134
/
Table 1
Summary of crystallographic data for complexes 7, 10 and 11
Although the reaction of 5 with PhSeCl did not yield a
stable phosphavinyl-selenium compound, it was decided
to pursue this aim by making modifications to the
aforementioned non-selective 1,2-additions of phenyl
selenyl halides to phosphaalkynes. To introduce more
control over the isomers formed in such reactions the
halide substituents in PhSeX were replaced with the
bulky phthalamide group. This strategy was successful
in that the reaction of N-phenylselenylphthalamide with
7
10
11
Formula
Mr
C22H40GaIP2
563.10
C34H50P2Se2
678.60
C19H18NO2PSe
402.27
˚
a (A)
9.5550(19)
10.915(2)
12.789(3)
98.13(3)
7.803(5)
23.040(15)
18.771(13)
90
13.370(3)
8.520(2)
16.175(3)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
PÅ
/
CBut in a 1:1 stoichiometry led regio- and stereo-
1105.11(3)
93.40(3)
1268.3(4)
92.620(18)
90
3371(4)
107.64(3)
90
specifically to the phosphavinyl-selenium compound,
11, in good yield (Scheme 2). The observed regiochem-
istry of the reaction is not surprising considering that the
triple bond of the phosphaalkyne starting material is
3
˚
V (A )
1755.9(7)
Monoclinic
Crystal sys- Triclinic
tem
Monoclinic
¯
Space
group
P/
1
/
P2(1)/c
P2(1)/c
polarised, dꢁPÅ
/
Cdꢂ, whilst the stereochemistry of the
˚
l (A)
0.71073
150(2)
2
0.71073
296(2)
4
0.71073
150(2)
4
addition is understandable on steric grounds.
T (K)
Z
All the spectroscopic data for 11 are consistent with
its proposed formulation which was confirmed by X-ray
crystallography. Its molecular structure (Fig. 3, Table 1)
shows the molecule to be monomeric with the phenylse-
Size
0.20ꢃ0.20ꢃ0.15 0.08ꢃ0.05ꢃ0.05 0.20ꢃ0.20ꢃ0.20
Colour
m (mmꢂ1
F(000)
Orange
2.433
572
Orange
2.309
Yellow
2.240
816
)
1408
15 544
lenyl group cis- to the phthalamide substituent. The
˚
C(1) bond length [1.687(3) A] is entirely consistent
Reflections 25 002
collected
3948
P(1)Ã
/
with a localised double bond and all other bond lengths
and angles are in the expected ranges. One feature of
note in the structure is the fact that the phenyl group
and the 5-membered ring of the phthalamide substituent
Unique re- 5794
flections
4844
3561
Parameters 241
varied
344
220
R
0.0280
0.0787
0.2184
0.0405
0.0901
are intramolecularly ‘stacked’ with a centroidÁcentroid
/
{I ꢀ2s(I)}
Rw {all
data}
˚
distance of 3.335 A (Fig. 3b) which is consistent with
0.0648
previously reported p-stacking interactions [18].
with a characteristic one bond coupling (1JSeP
Hz). We believe the mechanism of the reaction involves
ꢀ287
/
3. Conclusions
the initial formation of the selenophosphaalkene, CyPÄ
/
C(But)(SePh), which gives rise to the singlet at 320 ppm.
This rearranges, perhaps via a 1,2-selenyl shift to give a
In conclusion, the preparation and characterisation of
a range of phosphavinyl complexes that could prove
useful as reagents in organophosphorus synthesis have
been investigated. This study has led to the formation of
a series of terminal mono-phosphavinyl boron, tin and
selenium compounds, in addition to a new 1,3-l5,l5-
diphosphete. We are currently investigating the use of
short lived l5-phosphaalkyne, (Cy)(PhSe)PÅ
which was not detected by NMR spectroscopy but
/
CBut,
undergoes a spontaneous [2ꢁ2] cycloaddition reaction
/
to give 10. This mechanism seems reasonable as there is
precedent for the formation of l5,l5-diphosphetes via
the cycloaddition of l5-phosphaalkynes [16].
The molecular structure of 10 is depicted in Fig. 2
(Table 1). The data for this crystal structure were poor
due to the small size of the crystal used in the diffraction
experiment and, therefore, the accuracy of the metrical
parameters must be considered as low. Despite this, the
structure shows the compound to contain a central
the prepared phosphavinyl complexes in CÃ
/
C bond
forming reactions (e.g. Stille and Suzuki couplings) and
will report on this study in a forthcoming publication.
4. Experimental
All manipulations were carried out using standard
Schlenk and glove box techniques under an atmosphere
of high purity argon or dinitrogen. Toluene, Et2O, THF
planar four-membered PCPC ring in which all the PÃ
/
C
˚
bond lengths are of a similar magnitude (1.736 A avge.)
and in the range expected for delocalised PÃC double
/
and hexane were distilled over potassium or NaK alloy
1
then freezeÁ
/
thaw degassed prior to use. H-, 13C- and
bonds [12]. The geometry about the ring carbon atoms is
trigonal-planar and the phosphorus centres have dis-
torted tetrahedral environments, as is the case in the few
31P-NMR spectra were recorded on either a Bruker
DPX400 or JEOL Eclipse 300 spectrometer in C6D6 and
l5,l5-diphosphetes,
e.g.
1
were referenced to the residual H or 13C resonances of
previously reported
{(PhCH2)(Et2N)PC(Ph)}2 [17].
the solvent used (1H- and 13C-NMR) or to external 85%

S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á
/134
131
˚
Fig. 2. Molecular structure of 10. Selected bond lengths (A) and angles (8): Se(1)Ã
1.736(13), Se(2)ÃP(2) 2.300(4), P(2)ÃC(6) 1.729(13), C(1)ÃP(1)ÃC(6) 91.7(6), C(1)Ã
88.2(6), C(6)ÃP(2)ÃC(1) 92.1(6), C(6)ÃP(2)ÃSe(2) 104.8(5), C(1)ÃP(2)ÃSe(2) 117.2(5), P(2)Ã
/
P(1) 2.304(4), P(1)Ã
P(1)ÃSe(1) 106.8(5), C(6)Ã
C(6)ÃP(1) 88.0(6).
/
C(1) 1.732(13), P(1)Ã
/
C(6) 1.746(13), C(1)Ã
/
P(2)
P(2)
/
/
/
/
/
/
/
P(1)ÃSe(1) 118.1(5), P(1)Ã
/
/
C(1)Ã
/
/
/
/
/
/
/
/
/
H3PO4, 0.0 ppm (31P-NMR). Mass spectra were re-
corded using a VG Fisons Platform II instrument under
APCI conditions. Melting points were determined in
sealed glass capillaries under argon, and are uncor-
rected. Elemental analyses were carried out at the
Warwick Analytical Service. Reproducible elemental
analyses of 8, 9 and 11 could not be obtained but the
NMR spectra of the crude products showed them to
extracted into hexane (10 ml). The solution was then
filtered and the solvent removed in vacuo to give a
colourless oily solid. This was sublimed at 110 8C (0.001
mmHg) to give 6 as a colourless solid (145 mg, 30%),
1
m.p. 57Á
/
59 8C; H-NMR (300.5 MHz, C6D6, 298 K) d
4
1.37 (d, 9H, JPH
ꢀ
/
1.7 Hz, But), 2.24Á
0.97 (m, 11H,
/
Cy), 6.79 (m, 2H, Ph), 7.08 (m, 2H, Ph); 31P-NMR
(121.7 MHz, C6D6, 298 K) d 322.3 (s, PÄ
/
C); 11B-NMR
(96.4 MHz, C6D6, 298 K) d 31.5 (s); 13C-NMR (75.6
have a purity of ꢀ98%. Compound 5 was prepared by a
/
1
MHz, C6D6, 298 K) d 198.3 (d, JPC
literature procedure [1]. All other reagents were used as
received.
ꢀ
/
45.0 Hz, PÄ
/
C),
148.2 (s, Ar), 122.9 (s, Ar), 112.5 (s, Ar), 41.0 (d, 1JPC
ꢀ
/
2
35.8 Hz, Cy), 41.2 (d, JPC
ꢀ16.1 Hz, CMe3), 31.8 (d,
/
2JPC
26.4 (d, JPC
185 ([Mꢁꢂ
ꢀ
/
13.8 Hz, Cy), 31.7 (d, JPC
ꢀ
/
15.0 Hz, CMe3),
9.2 Hz, Cy), 25.6 (s, Cy); MS APCI m/z
BO2C6H4], 20%), 115 ([PCyꢁ], 50%), 83
3
4.1. [(C6H4O2)B{C(But)Ä
/
PCy}] (6)
3
ꢀ
/
/
To a solution of bromocatecholborane (0.31 g, 1.58
mmol) in Et2O (20 ml) at ꢂ78 8C was added 5 (0.50 g,
([Cyꢁ], 95%); IR (Nujol) n cmꢂ1: 1170 (m), 1148 (m),
1124 (s), 1094 (s), 1079 (s), 1004 (m), 956 (w), 917 (w),
881 (w), 866 (w), 848 (w); microanalysis found: C 66.88,
H 8.00; Calc. for C17H24BO2P: C 67.58, H 8.01%.
/
1.58 mmol) in Et2O (20 ml). The resultant pale yellow
solution was warmed to room temperature (r.t.) and
filtered. Volatiles were removed in vacuo and the residue
Scheme 2.

132
S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á134
/
˚
Fig. 3. Molecular structure of 11. Selected bond lengths (A) and angles (8): N(1)Ã
/
P(1) 1.743(3), Se(1)Ã
/
C(1) 1.900(3), Se(1)Ã
/
C(6) 1.907(3), P(1)ÃC(1)
/
1.687(3), C(1)ÃSe(1)ÃC(6) 105.57(14), C(1)ÃP(1)ÃN(1) 105.87(15), C(2)ÃC(1)ÃP(1) 117.5(2), P(1)Ã
/
/
/
/
/
/
/
C(1)Ã
/
Se(1) 130.08(19).
4.2. [IGa{C(But)Ä
/
PCy}2] (7)
placed at ꢂ
/
30 8C to yield orangeÁbrown crystals of 7
/
(0.05 g, 14%, yield based on number of mmol of I2), m.p.
120 8C dec.; 1H-NMR (300.5 MHz, C6D5CD3, 298
Gallium metal (0.13 g, 1.86 mmol) and iodine (0.24 g,
0.93 mmol) were suspended in toluene (20 ml) and
placed in a ultrasonic bath for 30 min. The generated
118Á
/
4
K) d 1.34 (d, JPH
ꢀ
/
2.2 Hz, 18H, But), 2.81Á
1.05 (m,
/
22H, Cy); 31P-NMR (121.7 MHz, C6D6, 298 K) d 307.2
(s, PÄ
1JPC
44.3 (d, JPC
CMe3), 30.4 (d, JPC
Hz, Cy), 25.4 (s, Cy); MS APCI m/z 563 ([Mꢁ], 29%),
367 ([MꢁꢂGaI], 19%); IR (Nujol) n cmꢂ1: 1378 (s),
/
C); 13C-NMR (75.6 MHz, C6D6, 298 K) 226.0 (d,
white suspension was cooled to ꢂ78 8C and 5 (0.60 g,
/
2
1.86 mmol) in toluene (20 ml) was added over 10 min.
The resultant red suspension was warmed to r.t. and
filtered. Volatiles were removed in vacuo and the residue
extracted into hexane (10 ml). The solution was then
filtered and the extract was concentrated to ca. 3 ml and
ꢀ
/
64.6 Hz, PÄ
/
C), 44.5 (d, JPC
ꢀ12.7 Hz, CMe3),
/
1
3
ꢀ
/
36.9 Hz, Cy), 33.0 (d, JPC
ꢀ16.1 Hz,
/
2
3
ꢀ
/
12.7 Hz, Cy), 26.0 (d, JPC
ꢀ8.1
/
/

S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á
/134
133
1358 (s), 1265 (m), 1230 (m), 1211 (w), 1190 (m), 1168
(w), 1090 (m), 1025 (m), 997 (m), 922 (s), 881 (m), 849
(s), 812 (w), 783 (w), 737 (w); microanalysis found: C
46.31, H 7.11; Calc. for C22H40GaIP2: C 46.93, H 7.16%.
4.5. [{(But)CP(Cy)(SePh)}2] (10)
To a solution of PhSeCl (0.30 g, 1.58 mmol) in Et2O
(20 ml) at ꢂ78 8C was added 5 (0.50 g, 1.58 mmol) in
/
Et2O (10 ml) over 10 min. The resultant orange solution
was warmed to r.t. and filtered. Volatiles were removed
in vacuo and the residue extracted into hexane (10 ml).
The solution was then filtered and the solvent reduced to
4.3. [Me3Sn{C(But)Ä
/
PCy}] (8)
A solution of Me3SnCl (0.32 g, 1.58 mmol) in Et2O
(20 ml) was cooled to ꢂ78 8C and 5 (0.50 g, 1.58 mmol)
in Et2O (10 ml) was added over 10 min. The resultant
pale orangeÁyellow solution was warmed to r.t. and
5 ml and placed overnight at ꢂ
orangeÁred crystals (0.43 g, 78%), m.p. 78Á
1H-NMR (300.5 MHz, C6D6, 298 K) d 1.40 (s, 18H,
/
30 8C to give 10 as
/
/
/
80 8C (dec.);
/
But), 2.36Á
1.03 (m, 22H, Cy), 6.99 (m, 2H, Ph), 7.84 (m,
/
filtered. Volatiles were removed in vacuo and the residue
extracted into hexane (10 ml). This was then filtered and
the solvent removed in vacuo to give 8 as a colourless
4H, Ph), 8.07 (m, 4H, Ph); 31P-NMR (121.7 MHz,
1
C6D6, 298 K) d 45.2 (s, JPSe
ꢀ
287 Hz, CPC); 13C-
NMR (75.6 MHz, C6D6, 298 K) d 139.4 (s, Ph), 137.7 (s,
/
1
liquid (0.50 g, 91%), H-NMR (300.5 MHz, C6D6, 298
Ph), 128.7 (s, Ph), 128.4 (s, Ph), 47.3 (d, 1JPC
ꢀ20.8 Hz,
/
2
2
3
K) d 0.33 (s, 9H, JSnH
ꢀ
/
25.9 Hz, SnMe3), 1.29 (d, 9H,
1.10 (m, 11H, Cy); 31P-NMR
(121.7 MHz, C6D6, 298 K) d 325.2 (s, 2JSnP
156.7 Hz,
Cy), 42.0 (t, JPC
ꢀ
/
17.3 Hz, CMe3), 34.8 (t, JPC
8.1 Hz, Cy), 26.3
P resonance not observed); MS APCI m/z
ꢀ8.1
/
4JPH
ꢀ
/
2.2 Hz, But), 2.34Á
/
Hz, CMe3), 28.1 (s, Cy), 27.2 (t, 3JPC
ꢀ
/
ꢀ
/
(s, Cy) (PÃ
/
C Ã
/
PÄ
/
C); 119Sn-NMR (112.1 MHz, C6D6, 298 K) d ꢂ
/
60.3
156.7 Hz); 13C-NMR (75.6 MHz, C6D6, 298
679 ([Mꢁ], 100%); IR (Nujol) n cmꢂ1: 1574 (m), 1263
(s), 1207 (w), 1167 (m), 1097 (w), 1035 (m), 1021 (m),
997 (w), 906 (m), 871 (m), 811 (w); Accurate mass MS
(EI) calc. mass for C34H50P2Se2: 680.1718, measured
mass: 680.1722.
2
(d, JSnP
ꢀ
/
1
K) d 219.5 (d, JPC
ꢀ
/
68.1 Hz, PÄ
/
CÃ
36.9 Hz, Cy),
18.5 Hz, CMe3), 31.5 (d, 2JPC
13.8 Hz,
9.2 Hz, Cy), 25.7 (s, Cy), ꢂ3.2 (d,
160.4 Hz, 3JPC
6.9 Hz, SnMe3); MS APCI m/z
263 ([MꢁꢂCy], 100%), 231; IR (Nujol) n cmꢂ1: 1447
/
Sn), 43.9 (d,
2JPC
32.2 (d, 3JPC
ꢀ
/
16.2 Hz, CMe3), 43.8 (d, JPC
ꢀ
/
1
ꢀ
/
ꢀ
/
3
Cy), 26.5 (d, JPC
ꢀ
/
/
1JSnC
ꢀ
/
ꢀ
/
4.6. [(C8H4O2N)PÄ
/
C(But)(SePh)] (11)
/
(s), 1388 (w), 1358 (s), 1260 (s), 1223 (m), 1188 (m), 1168
(w), 1096 (m), 1017 (m), 997 (w), 907 (w), 848 (m), 773
(s), 711 (m).
To a THF solution (10 ml) of N-phenylselenylphtha-
lamide (0.50 g, 1.67 mmol) at ꢂ
/
78 8C was added PÅ
/
CBut (0.27 ml, 1.67 mmol) over 5 min. The reaction
mixture was warmed slowly to r.t. and stirred for 48 h.
Removal of volatiles in vacuo and extraction into
hexane (5 ml) afforded 11 as pale yellow crystals after
4.4. [Bun3Sn{C(But)Ä
To a solution of Bun3SnCl (120 ml, 1.58 mmol) in Et2O
/
PCy}] (9)
placement at ꢂ
/
30 8C overnight. (0.42 g, 62%), m.p.
132 8C; H-NMR (300.5 MHz, C6D5CD3, 298 K)
d 1.05 (s, 9H, But), 6.32Á
6.61 (m, 5H, Ph), 7.22Á7.83
(m, 4H, ArH); 31P-NMR (121.7 MHz, C6D6, 298 K) d
237.7 (s, PÄ
C); 13C-NMR (75.6 MHz, C6D6, 298 K)
180.1 (s, CÄ 64.2 Hz, PÄC), 137.4 (s,
O), 166.0 (d, 1JPC
Ph), 136.9 (s, CCO), 135.2 (s, Ph), 130.2 (s, ArH), 126.7
1
129Á
/
(20 ml) at ꢂ78 8C was added 5 (0.20 g, 1.58 mmol) in
/
/
/
Et2O (10 ml) over 10 min. The resultant pale orangeÁ
/
yellow solution was warmed to r.t. and filtered. Volatiles
were removed in vacuo and the residue extracted into
hexane (10 ml). This was then filtered and the solvent
removed in vacuo to give 9 as a colourless liquid (0.22 g,
/
/
ꢀ
/
/
2
(s, Ph), 128.1 (s, Ph), 120.8 (ArH), 43.1 (d, JPC
3
Hz, CMe3), 32.0 (d, JPC
ꢀ/11.7
1
74%), H-NMR (300.5 MHz, C6D6, 298 K) d 0.96 (m,
9H, Bun), 1.14 (m, 6H, Bun), d 1.34 (d, 9H, JPH
ꢀ
/
15.2 Hz, CMe3), MS APCI
m/z 245 ([MꢁꢂPhSe], 10%), 156 ([PhSeꢁ], 100%); IR
4
ꢀ
/
2.8
Hz, But), 1.36 (m, 6H, Bun), d 1.58 (m, 6H, Bun), 2.41Á
/
/
(Nujol) n cmꢂ1: 1576 (m), 1276 (m), 1021 (m), 734 (m).
0.71 (m, 11H, Cy); 31P-NMR (121.7 MHz, C6D6, 298 K)
2
d 324.8 (s, JSnP
ꢀ
/
144.3 Hz, PÄ
/
C); 119Sn-NMR (112.1
4.7. Crystallographic studies
MHz, C6D6, 298 K) d ꢂ
/
54.2 (d, 2JSnP
ꢀ
144.3 Hz); 13C-
/
NMR (75.6 MHz, C6D6, 298 K) d 218.9 (d, 1JPC
ꢀ
/
69.2
Crystallographic measurements were made using
either an Nonius Kappa CCD (7), Siemens SMART
CCD (10) or an Enraf-Nonius CAD4 diffractometer
(11). All structures were solved using direct methods and
refined on F2 by full-matrix least-squares (SHELX-97)
[19] using all unique data. All non-hydrogen atoms are
anisotropic with H-atoms included in calculated posi-
tions (riding model). The data for the structure of
compound 10 were weak and poor due to the small
1
Hz, PÄ
/
CÃ
/
Sn), 43.8 (d, JPC
ꢀ
/
40.4 Hz, Cy), 43.5 (d,
18.5 Hz, CMe3),
13.8 Hz, Cy), 29.4 (s, Bun), 27.6 (s, Bun),
9.2 Hz, Cy), 25.8 (s, Cy), 14.5 (s, Bun),
2JPC
ꢀ
/
16.1 Hz, CMe3), 32.5 (d, 3JPC
ꢀ
/
31.6 (d, 2JPC
26.7 (d, JPC
ꢀ
/
3
ꢀ
/
13.6 (s, Bun); MS APCI m/z 473 ([Mꢁ], 11%); IR
(Nujol) n cmꢂ1: 1464 (s), 1448 (s), 1417 (w), 1388 (w),
1376 (m), 1359 (m), 1262 (w), 1206 (m), 1151 (s), 1072
(s), 1016 (s), 961 (m), 876 (w), 849 (w), 813 (s).

134
S. Aldridge et al. / Journal of Organometallic Chemistry 665 (2003) 127Á134
/
size of the crystal and repeated attempts to grow larger
crystals met with failure. However, the fact that all the
spectroscopic data for this compound are consistent
with its formulation leaves no doubt about the gross
molecular framework of the compound.
References
[1] D.E. Hibbs, C. Jones, A.F. Richards, J. Chem. Soc. Dalton
Trans. (1999) 3531.
[2] C. Jones, A.F. Richards, J. Chem. Soc. Dalton Trans. (2000)
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5. Supplementary material
[5] C. Jones, A.F. Richards, S. Fritzsche, E. Hey-Hawkins, Organo-
metallics 21 (2002) 438.
[6] M. Brym, C. Jones, A.F. Richards, J. Chem.Soc. Dalton Trans.
(2002) 2800.
Crystallographic data (excluding structure factors) for
the structures of 7, 10 and 11 have been deposited with
the Cambridge Crystallographic Data Centre (7: CCDC
no. 193028; 10: CCDC no. 193029, 11: CCDC no.
193030). Copies of this information may be obtained
free of charge from The Director, CCDC, 12 Union
[7] E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.), Comprehensive
Organometallic Chemistry II, vol. 11, Pergamon, Oxford, 1995.
[8] N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457 (and
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[9] A.J. Downs (Ed.), Chemistry of Aluminium, Gallium and
Thallium, Blackie Academic, Glasgow, 1993.
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/
[10] C. Jones, J.A. Platts, A.F. Richards, Chem. Commun. (2001) 663.
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9 (1990) 2763.
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www.ccdc.cam.ac.uk).
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Sulfur Silicon 130 (1997) 23.
Acknowledgements
[16] B. Neumuller, E. Fluck, Phosphorus Sulfur 29 (1986) 23.
¨
[17] E. Fluck, R. Braun, A. Muller, H. Bogge, Z. Anorg. Allg. Chem.
¨
We gratefully acknowledge support from the EPSRC
(studentship for A.F.R, postdoctoral fellowship for
M.W.). Thanks also go to the EPSRC Mass Spectro-
metry Service, Swansea, UK for the accurate mass
determination of compound 10.
609 (1992) 99.
[18] e.g. C.A. Hunter, J.K.M. Sanders, J. Am. Chem. Soc. 112 (1990)
5525.
[19] G.M. Sheldrick, SHELX-97, University of Gottingen, 1997.
¨