The crystal structure of [Mo(NCS)(CO)2(η3-C3H5) (NCMe)2].MeCN and the reactions of {Mo(CO)2 (η3-C3H5)+} containing species with symmetric alkynes

Article abstract of DOI:10.1016/S0022-328X(02)01981-2

In the solid-state about molybdenum, with carbonyls and nitriles in the equatorial plane and an N-bonded thiocyanate group trans to the allyl ligand. In refluxing methanol or acetonitrile both 1, and the analogous chloro-complex [MoCl(CO)₂(η³-C₃ H₅)(NCMe)₂](2) catalytically convert PhC≡CPh to a mixture of hexaphenylbenzene and E,E-1,2,3,4-tetraphenylbutadiene. By contrast MeO₂CC≡CCO₂Me is not oligomerised. In methanol, complex 2 dimerises 1,4-diphenylbutadiyne to Z,E-1,4,5,8-tetraphenyl-1,7-octa-3,5-diene-1,7-diyne, whereas in the presence of base both the complex and the diyne, react preferentially with the solvent to generate the [Mo₂(CO)₄ (η³-C₃H₅)₂ (OMe)₃]^- anion and Z-1,4-diphenyl-3- methoxy-but-3-ene-1-yne, respectively.

Full text of DOI:10.1016/S0022-328X(02)01981-2

Journal of Organometallic Chemistry 664 (2002) 176ꢄ181
/
www.elsevier.com/locate/jorganchem
The crystal structure of [Mo(NCS)(CO)2(h3-C3H5)(NCMe)2]×
/
MeCN
and the reactions of {Mo(CO)2(h3-C3H5)ꢀ} containing species with
symmetric alkynes
Jonathan W. Goodyear a, Clive W. Hemingway a, Ross W. Harrington a,b,ꢁ,
Matthew R. Wiseman a, Brian J. Brisdon a
a Department of Chemistry, University of Bath, Bath BA2 7AY, UK
b Department of Chemistry, University of Newcastle, Bedson Building, Newcastle-upon-Tyne, Newcastle NE1 7RU, UK
Received 16 August 2002; received in revised form 30 September 2002; accepted 30 September 2002
Abstract
In the solid-state [Mo(NCS)(CO)2(h3-C3H5)(NCMe)2] ×
/
MeCN (1) contains a pseudo-octahedral arrangement of ligands about
molybdenum, with carbonyls and nitriles in the equatorial plane and an N-bonded thiocyanate group trans to the allyl ligand. In
refluxing methanol or acetonitrile both 1, and the analogous chloro-complex [MoCl(CO)2(h3-C3H5)(NCMe)2] (2) catalytically
convert PhCꢀ
/
CPh to a mixture of hexaphenylbenzene and E,E-1,2,3,4-tetraphenylbutadiene. By contrast MeO2CCꢀ
/
CCO2Me is
not oligomerised. In methanol, complex 2 dimerises 1,4-diphenylbutadiyne to Z,E-1,4,5,8-tetraphenyl-1,7-octa-3,5-diene-1,7-diyne,
whereas in the presence of base both the complex and the diyne, react preferentially with the solvent to generate the [Mo2(CO)4(h3-
C3H5)2(OMe)3]ꢂ anion and Z-1,4-diphenyl-3-methoxy-but-3-ene-1-yne, respectively.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Molybdenum(II)allyl; Solid-state structure; Alkyne and diyne oligomerisation
1. Introduction
fluxional processes in solution [3], and novel hetero-
nuclear molybdenum/bismuth alkoxides of interest as
models of propene oxidation catalysts [4].
Molybdenum(II) complexes of the type [MoX-
(CO)2(h3-allyl)(NCMe)2] (Xꢃ
The h3-allyl group in several {Mo(CO)2(h3-allyl)ꢀ}
containing species has also been shown to be susceptible
to highly regioselective as well as entioselective reactions
[5], and subsequently routes to stoichiometric and
catalytic allylic alkylations which involve Mo(0)/
Mo(II)-allyl intermediates, have been reported [6].
More recently stoichiometric alkyne-allyl coupling reac-
tions have been demonstrated for two dithiophosphinate
/
halide or pseudohalide)
have been used extensively over several decades as
synthetic precursors for a wide variety of Mo(II)-allyl
derivatives containing the 12eꢂ {Mo(CO)2(h3-allyl)ꢀ}
fragment, which are formed by substitution of the labile
nitrile ligands and/or the anion X [1]. This group of
compounds includes the historically significant complex
[Mo(CO)2(h3-allyl)(Bpyr2Et2)] {Bpyr2Et2ꢃ
pyrazolyl)borato anion}, which provided the first struc-
turally characterised example of a molecular species
/(3,5-diethyl-
derivatives, [Mo(CO)2(h3-allyl)(S2PX2)(MeCN)] (Xꢃ
/
OEt, Ph), resulting in the formation of intramolecularly
stabilised s-alkenyl complexes [7]. Reductive elimina-
tion of allyl halides from [MoX(CO)2(h3-allyl)(NCMe)2]
also provides a facile entry into electron-rich Mo(0)-
with a Cꢄ
/
HÁ Á ÁM agostic interaction [2], some pyridyl-
phosphane derivatives which exhibit three independent
?
dicarbonyl species, [Mo(CO)2L4] and [Mo(CO)2L2L2],
ꢁ Corresponding author. Tel.: ꢀ
222-6929
E-mail address: r.w.harrington@ncl.ac.uk (R.W. Harrington).
/
44-191-222-6641; fax: ꢀ44-191-
/
which are not available by direct substitution in
Mo(CO)6 [8].
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 1 9 8 1 - 2

J.W. Goodyear et al. / Journal of Organometallic Chemistry 664 (2002) 176ꢄ
/181
177
2. Results and discussion
2.1. Structural studies on [Mo(NCS)(CO)2(h3-
C3H5)(NCMe)2] × MeCN (1)
/
Scheme 1. The structural isomers of [MoX(CO)2(h3-allyl)L2] com-
pounds.
Complex 1 was prepared in good yield by the reaction
of Mo(CO)6 with allyl thiocyanate in refluxing acetoni-
trile. Crystals of 1 suitable for an X-ray structure
determination were obtained directly from the cooled
reaction solution. The structure of 1, showing the atom-
labelling scheme used, is shown in Fig. 1. The molecular
unit possesses a mirror plane, and the geometry about
molybdenum can be described as pseudooctahedral with
carbonyl and nitrile ligands in the equatorial plane, and
an N-bonded thiocyanate trans to the allyl group.
Significant bond lengths and angles are given in Table
1. Compared with other known complexes of the type
[Mo(halide)(CO)2(h3-C3H5)(N-donor)2] which adopt
structural type (A) [9,10], the bond lengths and angles
The structures of many complexes in which the nitrile
ligands in [MoX(CO)2(h3-allyl)(NCMe)2] have been
replaced by stronger s-donors have been reported in
the literature [9]. They all adopt one of the three basic
structures (A)ꢄ(C), illustrated in Scheme 1. Structural
/
types (A) and (B) are most frequently found, and these
are conveniently described as pseudooctahedral with the
allyl ligand occupying a single coordination site. How-
ever, if the h3-allyl ligand is regarded as occupying two
coordination sites, then all three structural types can be
related either to the capped trigonal-prismatic or the
pentagonal-bipyramidal structures commonly found for
other seven-coordinate species.
Table 1
˚
Selected bond lengths (A) and bond angles (8) for complex 1
Of the parent nitrile species, [MoX(CO)2(h3-
C3H5)(NCMe)2], whose reactions lead to products with
this extremely wide variety of different structural motifs,
dynamic behaviour, and synthetic applications, only the
structure of the bromo derivative has been reported [10].
In this investigation a single crystal X-ray study of the
thiocyanate derivative, 1, has been undertaken, and the
reactions between 1, and its chloro-analogue, 2, with
diphenylacetylene, dimethyl acetylenedicarboxylate and
1,4-diphenylbutadiyne have also been elucidated.
Bond lengths
Mo(1)ꢄ
Mo(1)ꢄ
Mo(1)ꢄ
/
N(1)
C(4)
C(6)
2.157(4)
1.950(4)
2.212(5)
1.154(7)
1.617(5)
Mo(1)ꢄ
/
N(2)
C(5)
2.243(3)
2.333(3)
1.397(5)
1.134(5)
1.444(5)
/
Mo(1)ꢄ
/
/
C(5)ꢄ
C(2)ꢄ
C(2)ꢄ
/
C(6)
N(2)
C(3)
C(1)ꢄ
/
N(1)
S(1)
/
C(1)ꢄ
/
/
Bond angles
N(1)ꢄMo(1)ꢄ
N(2)ꢄMo(1)ꢄ
N(2)ꢄMo(1)ꢄ
C(5)ꢄC(6)ꢄ
/
/
N(2)
N(2)?
C(4)
83.37(12) N(1)ꢄ
81.6(2) C(4)ꢄMo(1)ꢄ
97.92(14) Mo(1)ꢄN(1)ꢄ
/
Mo(1)ꢄ
/
C(4)
89.88(14)
81.5(2)
173.8(4)
/
/
/
/C(4)?
/
/
/
/C(1)
/
/C(5)?
116.5(5)
Fig. 1. The structure of [Mo(NCS)(CO)2(h3-C3H5)(NCMe)2] ×
/
MeCN (1).

178
J.W. Goodyear et al. / Journal of Organometallic Chemistry 664 (2002) 176ꢄ181
/
in the primary coordination sphere of the metal and in
the h3-bonded propenyl group are unexceptional,
Column separation of the organic products afforded
1,2,3,4-tetraphenylbutadiene, 3, and hexaphenylben-
zene, 4. Both the melting point and the NMR spectra
of the diene showed it to be the E,E-isomer. Although
the yields of the two products 3 and 4 were slightly
dependent upon the metal complex, Ph6C6 was consis-
tently the major product. Reactions carried out in
methanol for a shorter period of time, or at room
temperature, failed to produce any new, isolable organic
products or metal complexes. Therefore, the reaction
between 2 and diphenylacetylene was repeated using
acetonitrile as solvent. Reaction at reflux temperatures
again produced a mixture of hexaphenylbenzene and
1,2,3,4-tetraphenylbutadiene. Under less forcing condi-
tions only starting materials were isolated from the
reaction mixtures.
˚
N(1) separation at 2.157(4) A is
although the Moꢄ
/
˚
slightly greater than that of 2.119(7) A found in the
only other structurally characterised thiocyanate analo-
gue containing an unsubstituted allyl ligand, [Mo(N-
CS)(CO)2(h3-C3H5)(2,2?-bipyridine)]
[11].
compounds contain an almost linear Moꢄ
Both
NꢄCꢄS
arrangement. There are no abnormally short contacts
/
/
/
involving the lattice solvent molecule, which has a
shortened Cꢄ
/
N and a lengthened Cꢄ
/
C bond [C(7)ꢄ
/
˚
N(3)ꢃ1.101(11) and C(7)ꢄ
/
/
C(8)ꢃ1.423(14) A, respec-
/
tively], compared to those in the coordinated MeCN in 1
(Table 1).
On dissolution in deuterated methanol only a single
set of signals was apparent in the proton NMR
spectrum of 1, whereas in deuterated acetonitrile a
second, weaker set of allyl signals with chemical shifts
and coupling constants appropriate for the known
[Mo(CO)2(h3-C3H5)(MeCN)3]ꢀ cation [12,13] were
also present. Addition of AgBF4 resulted in precipita-
tion of AgNCS and an increase in the intensity of the
weaker set of signals due to the cationic species. Thus
partial solvolysis of 1 occurs in acetonitrile as indicated
in the equation below.
Even at ambient temperature there was a slow colour
change from yellow to brown on reacting C2(CO2Me)2
with a solution of 1 or 2 in methanol. The alkene
MeCO2C(OMe)ꢁ
/
CH(CO2Me) (5) was isolated in good
yield from heated solutions, and small quantities of a
second product, 6, were also isolated from some
reactions. This was shown to be MeCO2C(C3H5)ꢁ
/
CH(CO2Me) and it was the only organic product
incorporating the allyl group found in this study. It
has been reported previously [7] that the allyl ligand in
[MoNCS(CO)2(h3-C3H5)(MeCN)3]ꢀMeCN 0
[Mo(CO)2(h3-C3H5)(MeCN)3]ꢀ ꢀNCSꢂ
[Mo(CO)2(h3-C3H5)(NCMe)(S2PX2)], Xꢃ
/
OEt or Ph,
couples with dimethyl acetylenedicarboxylate to form a
metal complex which decomposes on exposure to moist
air yielding dimethyl 2-allylfumurate. It appears that a
similar allyl-alkyne coupling reaction may occur above,
and that the excess alkyne present in the reaction
mixture reacts with the solvent. On using acetonitrile
instead of methanol as solvent, unreacted C2(CO2Me)2
was recovered, but we were unsuccessful in isolating any
intermediate metal complex.
The extreme solvent dependency of [MoCl(CO)2(h3-
C3H5)(NCMe)2] (2) has been described previously
[12,13]. Auto-ionisation as described by the equation
below occurs at room temperature in non-protonic
solvents, including acetonitrile, and the ionic compound
[Mo(CO)2(h3-C3H5)(NCMe)3][Mo2Cl3(CO)4(h3-
C3H5)2], which has been structurally characterised [14],
was obtained by recrystallisation of [MoCl(CO)2(h3-
C3H5)(NCMe)2] from dry benzene.
Column separation of the products of the reaction in
boiling methanol between 1 or 2 and 1,4-diphenylbuta-
diyne yielded small quantities of unreacted diyne and
yellow crystals of a single ene-yne product formed by
diyne dimerisation. Of the two possible isomers, NMR
3[MoCl(CO)2(h3-C3H5)(NCMe)2]0 3MeCN
ꢀ[Mo(CO)2(h3-C3H5)(NCMe)3]ꢀ
ꢀ[Mo2Cl3(CO)4(h3-C3H5)2]ꢂ
measurements confirmed that the E,Z-isomer of PhCꢀ
CC(H)ꢁCPhCPhꢁC(H)CꢀCPh (7b) had been formed,
albeit in quite low yield.
Addition of base to the above reaction completely
altered the nature of the reaction. Here, no new Cꢄ
/
In protic solvents, including methanol and water,
NMR studies have shown that only a single allyl-
containing species is formed [15]. The spectra of 1 and
2 do not change in methanolic solutions on heating in
the absence of air, and consequently this solvent was
preferred for our initial studies of the alkyne reactions.
/
/
/
/C
bond formation occurred, and instead MeOH added
across one of the acetylenic bonds of the diyne. Of the
four possible isomers, chemical shifts of nOe measure-
ments indicated that the Z-isomer of 1,4-diphenyl-3-
methoxy-but-3-ene-1-yne (8a), was formed. The same
product was formed in 90% yield in the absence of the
metal complex, confirming that nucleophilic addition
across a single triple bond in 1,4-diphenylbutadiyne is
not affected by the presence of the metal species, which
in this case is the known [15] [Mo2(OMe)3(CO)4(h3-
2.2. Alkyne and diyne reactions
Reactions in refluxing methanol between complex 1
or 2 and excess diphenylacetylene were complete in 24
hours, by which time the metal complex had lost its
catalytic activity, and solution infrared measurements
showed that no metal carbonyl species remained.

J.W. Goodyear et al. / Journal of Organometallic Chemistry 664 (2002) 176ꢄ
/181
179
described above, but in hot methanol both complexes
C)nPh, where nꢃ1 or 2, but not
C2(CO2Me)2. Under similar reaction conditions
oligomerise Ph(Cꢀ
/
/
[MoCl(CO)2(h3-C3H5)(2,2?-dipyridyl)] is inactive.
4. Experimental
4.1. General
Acetonitrile was distilled over calcium hydride under
a dry nitrogen atmosphere immediately prior to use.
Other solvents were dried over molecular sieves (type
4A). Allyl isothiocyanate and allyl chloride purchased
from commercial sources were distilled and dried over
molecular sieves. Column chromatography was carried
out using silica gel or fluorosil. The starting material
[MoCl(CO)2(h3-allyl)(NCMe)2] (2) was prepared in 80%
yield either by Hayter’s method [17], or a modification
thereof [13]. Infra-red analyses were carried out using a
C3H5)2]ꢂ ion, formed by the reaction of methoxide with
2. This metal-containing cation could be isolated as a
tetraalkylammonium salt from basic methanolic solu-
tions of either 1 or 2 in the presence or absence of the
diyne.
Nicolet 510P or PerkinꢄElmer 1600 FT-IR spectrometer
/
on solid samples mulled with Nujol between sodium
chloride discs; liquid samples were suspended between
NaCl discs. Elemental microanalyses were determined
by the Departmental Microanalytical Services Unit
using a Carloꢄ
Erba 1106 analyser. Proton and 13C-
/
NMR spectra were recorded on JEOL 270 and EX400
instruments using CDCl3 as solvent and tetramethylsi-
lane as internal reference. Shift values are given in ppm.
Mass spectral data were obtained using a VG 7070E
instrument.
4.2. Synthesis
4.2.1. Preparation of [Mo(NCS)(CO)2(h3-
C3H5)(MeCN)2] ×
/
MeCN (1)
Mo(CO)6 [2.64 g (10.0 mmol)] was added to a stirred
acetonitrile (25 cm3) solution of allyl thiocyanate (3.0
cm3, 28.0 mmol). The clear solution was heated under
reflux for 3.5 h in an atmosphere of nitrogen gas. At the
end of the reaction the solvent volume was reduced by
half, and the deep orange solution cooled and held at
0 8C for 12 h. Bright yellow X-ray quality crystals of 1
were isolated by filtration, washed with ice-cold aceto-
nitrile and stored under an inert atmosphere. Yield 2.34
g (78%). Anal. Found: C, 38.5; H, 3.72; N, 14.75. Calc.
for C12H14MoN4O2S: C, 38.5; H, 3.77; N, 14.95%. IR
(Nujol, cmꢂ1) nmax 2307 s (CN str, MeCN), 2280 s (CN
str, MeCN), 2094 vs (CN str, NCS), 1929 (CO str), 1848
(CO str). 1H-NMR (CD3CN), dppm 1.28 (d, 2 H,
3. Conclusions
There has been considerable interest in the reactivity
of seven-coordinate Mo(II) and W(II) complexes to-
wards alkenes and alkynes in the last two decades, and
several have been shown to act as homogeneous
catalysts for alkyne dimerisation and [2ꢀ
/
2ꢀ2] cycload-
/
dition reactions [16]. Surprisingly, considering that
complexes of the type [MoX(CO)2(h3-C3H5)(NCMe)2],
allylHanti, Jꢃ
3.39 (d, 2H allylHsyn, Jꢃ
intensity signals at 1.47 (d, Jꢃ
Hz) and 4.02 (tt, Jꢃ9.6 and 6.0 Hz) with relative
intensities 2:2:1 are assigned to allyl resonances of the
known [13] cationic species
[Mo(CO)2(h3-
/
9.8 Hz); 2.15 (s, 6H, MeCNcoordinated);
4.9 Hz); 3.84 (m, 1H). Low
9.6 Hz), 3.56 (d, Jꢃ6.0
/
where Xꢃ
/
halide or pseudohalide, have been known for
/
/
thirty years, this is the first report of their reactivity
towards alkynes. Studies of the reactivity of 1 and 2 are
complicated by their unusual solution behaviour as
/

180
J.W. Goodyear et al. / Journal of Organometallic Chemistry 664 (2002) 176ꢄ181
/
C3H5)(MeCN)3]ꢀ. In CD3OD the proton NMR spec-
trum of 1 in the allyl region was similar to that of 2 [13].
evaporation. Yield 0.27 g (24%). Anal. Found: C, 86.8;
H, 6.06. Calc. for C17H14O: C, 87.2; H, 6.02%. MS m/e
234. H-NMR: (CDCl3), dppm 4.20 (s, 3H, OMe), 5.55
1
4.3. Alkyne and diyne reactions
(s, 1H, CH), 7.40 (m, 10H, aromatics). 13C-NMR:
(CDCl3), dppm 163.7 (COMe), 133.8, 131.0, 129.2,
128.4, 128.3, 127.8, 125.9, 124.0 (aromatics), 93.6
(CHPh), 86.5 (CPh), 86.4 (CPh), 59.7 (OMe) The
same product was prepared in 90% yield in the absence
of a metal complex.
A solution of the alkyne or diyne (5.0 mmol) in
methanol (50 cm3) was treated with finely divided 1 or 2
(0.75 mmol), and then heated under reflux under a N2
atmosphere for 24 h. The cooled reaction mixture was
then treated as follows.
PhCꢀ
/
CPh * A light brown solid was removed by
/
filtration and shown by TLC to consist of two major
products. These were separated on a fluorosil column
eluted first with petrol/diethyl ether (3:1 v/v), and then
dichloromethane to remove the second product. Com-
pound 3, yield 0.30 g (34%); m.p. 182 8C (lit. [18]
184 8C). Anal. Found: C, 93.3; H, 6.14. Calc. for
C28H22: C, 93.9; H 6.18%. MS (70 eV) m/e 358.
Compound 4, yield 0.52 g (58%); m.p. 453 8C (lit. [19]
454 8C). Anal. Found: C, 94.2; H, 5.66. Calc. for
C42H30: C, 94.3; H, 5.65%. MS (70 eV) m/e 534.
4.4. X-ray crystallography
A crystal of 1 (0.3ꢅ
/
0.3ꢅ
0.2 mm3) was selected for
/
data collection. X-ray data was collected on an Enrafꢄ
/
Nonius CAD4 automatic four-circle diffractometer and
the structure solved using XCAD [20] and SHELX [21]
software. The asymmetric unit consists of half of one
organometallic molecule and half of one acetonitrile
molecule, with atoms Mo1, C5, H6, N1, C1, S1, C8, C7,
N3 and H8A seated on the mirror plane at yꢃ1/4 in the
space group.
/
MeO2CCꢀ
/
CCO2Me * The oily residue remaining
/
after removal of the solvent was eluted from a silica
column using first cyclohexane/ethyl acetate (9:1 v/v),
and then dichloromethane, to afford 5 and 6 as oils.
Yield of 5, 0.56 g (64%). Anal. Found: C, 48.2; H, 5.74.
Calc. for C7H10O5: C, 48.2; H, 5.75%. MS (70 eV) m/e
174. 1H-NMR: (CDCl3), dppm 3.76 (s, 3 H Me), 3.85 (s 3
H Me), 3.95 (s 3 H, Me), 6.19 (s 1 H, CH). 13C-NMR:
Table 2
Crystallographic data and structure refinement for 1
Empirical formula
Formula weight
Temperature (K)
C12H14MoN4O2S
374.27
293(2)
˚
Wavelength (A)
0.70930
Monoclinic
P21/m
(CDCl3), dppm 164.7 (CO2), 163.3 (CO2), 154.7 (C ꢁ
/
CH),
CH), 61.1 (Me), 52.9 (Me), 51.8 (Me). Yield of
Crystal system
Space group
Unit cell dimensions
107.7 (Cꢁ
/
6, 0.10 g (72%). Anal. Found: C, 39.0; H, 5.50. Calc. for
˚
a (A)
6.3530(10)
10.2580(10)
12.502(2)
90.97
1
C9H12O4: C, 39.5; H, 5.69%. MS (70 eV) m/e 184. H-
NMR: (CDCl3), dppm 6.76 (s, 1H CHCH2), 5.80 (m,
˚
b (A)
˚
c (A)
1CH) 5.10ꢄ
(d 2H, CH2, Jꢃ
PhCꢀCꢄCꢀCPh *
poration of the solvent was extracted with 2ꢅ
/
5.00 (m, 2H, Cꢁ
/CH2) 3.80 (s 6H Me), 3.50
b (8)
3
V (A )
˚
814.6(2)
2
1.526
/
16 Hz).
Z
/
/
/
/
The solid remaining after eva-
5 cm3 of
Dcalc (Mg mꢂ3
)
/
Absorption coefficient 0.938
(mmꢂ1
petrol and the combined extract columned on fluorosil
using petrol/diethyl ether (1:1 v/v) to elute unchanged
diyne, followed by petrol/dichloromethane (1:1 v/v) to
elute the yellow product 7. Yield 0.12 g (24)%, m.p.
232 8C. Anal. Found: C, 93.7; H, 5.46. Calc. for
)
F(000)
376
0.3ꢅ0.3ꢅ0.2
Crystal size (mm)3
u Range for data col-
lection (8)
2.56ꢄ26.91
/
Index ranges
Reflections collected
ꢂ85h 50; ꢂ125k 50; ꢂ155l 515
3522
1
C32H22: C, 94.5, H, 5.46%. MS (70 eV) m/e 406. H-
NMR: (CDCl3), dppm 6.65 (s, 1H, CH), 6.80 (s, 1H,
Independent reflections 1870 [Rintꢂ0.0055]
Refinement method
Data/restraints/para-
meters
Full-matrix least-squares on F2
1870/8/123
CH), 7.1ꢄ
8.0 (m, 20H, aromatics). 13C-NMR: (CDCl3),
dppm 152.3, 138.6, 137.8, 136.3, 131.6, 131.4, 130.2,
129.6, 128.7, 128.5, 128.2, 123.7, 123.1, 122.8, 110.8,
/
Goodness-of-fit on F2
Final R indices
[I ꢀ2s(I)]
1.090
R1ꢃ0.0468, wR2ꢃ0.1225
89.3 (ꢀ
/
CPh), 86.8 (ꢀ
/
C ꢄ
/
C).
The reaction was repeated as
PhCꢀ
/
CꢄCꢀCPh *
/
/
/
Largest difference peak 1.362 and ꢂ0.815
above using a solution of NaOH (0.40 g, 10 mmol) in
MeOH (50 cm3) as solvent. The reaction mixture was
evaporated to dryness; the residue treated with cyclo-
hexane (10 cm3) and the extract columned on fluorosil
to afford starting material followed by a yellow solution
from which crystal of product 8 were obtained on
ꢂ3
˚
and hole (e A
)
Weighting scheme
Calc wꢃ1/[s2(F2o)ꢀ(0.1000P)2ꢀ0.000P],
where Pꢃ(F2oꢀ2Fc2)/3
0.0050(29)
Extinction coefficient
Extinction expression
2
3
ꢂ1/4
ꢁ
Fc ꢃkFc[1ꢀ0.001ꢅFcl /sin(2u)]

J.W. Goodyear et al. / Journal of Organometallic Chemistry 664 (2002) 176ꢄ
/181
181
(d) A. Rubio, L.S. Liebeskind, J. Am. Chem. Soc. 115 (1993) 891;
(e) D. Dvorak, J. Stary, P. Kocovsky, J. Am. Chem. Soc. 117
(1995) 6130;
Full-matrix least-squares anisotropic refinement for
all non-H atoms yielded R1ꢃ0.0468 and wR2ꢃ0.1110
at convergence. Hydrogen atoms were included at
calculated positions where relevant, except in the case
of the allyl and solvent moieties. These positions were
located in the penultimate difference fourier map and
˚
positionally refined at a distance of 0.98 A from the
relevant parent atoms. Crystal data and refinement
details are given in Table 2.
/
/
(f) J.W. Faller, K.J. Chase, M.R. Mazzieri, Inorg. Chim. Acta 229
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5. Supplementary material
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 158092 for compound 1.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
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¨