Novel binary compounds of group 15 elements: Synthesis and characterisation of [Sb4(PSiMe2Thex)4], [Sb 4(AsSiiPr3)4] and [Sb2(PSiPh 2tBu)4]

Article abstract of DOI:10.1002/ejic.200400610

The low-temperature reactions of Me₂ThexSiPLi₂ (Thex = CMe₂iPr) and iPr₃SiAsLi₂ with SbCl ₃ in a 3:2 molar ratio yields the cage compounds [Sb ₄(PSiMe₂Thex)₄] (1) and [Sb ₄(AsSiiPr₃)₄] (2), respectively. The metal salt SbBr₃ reacts with tBuPh₂SiPLi₂ at -70 °C to give the bicyclic compound [Sb₂(PSiPh₂tBu)₄] (3). Compounds 1-3 were characterised by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction. The structures of 1 and 2 reveal that the both compounds adopt a structure similar to those of realgar (As₄S₄). The central structural motif is an Sb₄Y₄ cage (Y = P, As), consisting of four five-membered rings with common edges. The bicyclic compound 3 is composed of five-membered and three-membered rings sharing a common Sb₂ bridgehead. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400610

FULL PAPER
Novel Binary Compounds of Group 15 Elements: Synthesis and
Characterisation of [Sb4(PSiMe2Thex)4], [Sb4(AsSiiPr3)4] and
[Sb2(PSiPh2tBu)4]
Donna Nikolova[a] and Carsten von Hänisch*[a]
Keywords: Arsenic / Antimony / Cage compounds / Phosphorus
The low-temperature reactions of Me2ThexSiPLi2 (Thex =
CMe2iPr) and iPr3SiAsLi2 with SbCl3 in a 3:2 molar ratio similar to those of realgar (As4S4). The central structural motif
yields the cage compounds [Sb4(PSiMe2Thex)4] (1) and is an Sb4Y4 cage (Y = P, As), consisting of four five-membered
[Sb4(AsSiiPr3)4] (2), respectively. The metal salt SbBr3 reacts rings with common edges. The bicyclic compound 3 is com-
with tBuPh2SiPLi2 at −70 °C to give the bicyclic compound posed of five-membered and three-membered rings sharing
[Sb2(PSiPh2tBu)4] (3). Compounds 1−3 were characterised by a common Sb2 bridgehead.
of 1 and 2 reveal that the both compounds adopt a structure
NMR and IR spectroscopy, mass spectrometry, elemental
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
analysis and single-crystal X-ray diffraction. The structures
Germany, 2005)
Introduction
from the reactions of lithium phosphanides and arsanides
with the antimony salts SbCl3 and SbBr3, respectively.[7]
The formation of homonuclear cyclic, polycyclic and
cage-like compounds of group 15 elements has been the fo-
cus of intensive research efforts for a long time.[1Ϫ3] These
studies have revealed a very diverse range of structure types,
which extend from simple small rings like P3tBu3 [2] through
five- and six-membered rings, to polycycles and cages con-
taining up to fourteen atoms.[3] Few analogous binary com-
pounds containing a combination of heavier group 15 ele-
ments have been structurally characterised. Although not
as widely studied as the organophosphorus homocycles,
cyclic As/P and Sb/P compounds are known. The first P2As
heterocycle was synthesized by cyclocondensation of
tBu2P2K2 with tBuAsCl2.[4] Other reported species are the
bicyclic compounds [As2(PAr)2] and [Sb2(PAr)2], which are
obtained by the reaction of ArP(SiMe3)Li [Ar ϭ 2,4,6-
(tBu)3C6H2] with Cp*EЈCl2 (EЈ ϭ As, Sb) as well as
[(tBuP)3As]2 and [(tBuP)3Sb]2.[5] The most recent extension
of group 15 element chemistry is the formation of hetero-
cyclic compounds containing SbϪAs bonds. To the best of
our knowledge, the only structurally characterised Sb/As
heterocycle is the coordination complex [Sb2Cl6{o-
C6H4(AsMe2)2}].[6]
Results and Discussion
The reaction of Me2ThexSiPLi2 (Thex ϭ CMe2iPr) with
SbCl3 in a 3:2 molar ratio leads to the formation of 1, which
can be isolated as orange crystals by cooling the reaction
mixture to Ϫ35 °C. Compound 1 crystallises in the ortho-
rhombic space group P42/n. The central structural motif is
an Sb4P4 cage (Figure 1). It consists of four Sb3P2 five-
membered rings with common SbϪPϪSb edges. The struc-
ture can be thought of as being derived from an Sb4 tetra-
hedron by placing bridging PSiMe2Thex fragments above
four of the six edges. All of the phosphorus atoms are coor-
dinated to two antimony atoms and one ThexMe2Si group,
forming a trigonal-pyramidal environment; the Sb atoms
possess no exocyclic ligands and also have a coordination
number of three. The availability of the SbϪSb bonds
(Sb1ϪSb1ЈЈ and Sb1ЈϪSb1ЈЈЈ) in the molecule is indicative
of a reduction process that must have taken place parallel to
the lithium chloride elimination reaction. The SbϪSb bond
length in 1 is 287.9 pm, which is in the usual range for
single SbϪSb bonds. Similar SbϪSb bond lengths of 286.7
pm, for example, can be observed in Sb2(SiMe3)4,[8] whereas
in the polycycles Sb8R6 and Sb8R4 [R ϭ CH(SiMe3)2] these
bonds are slightly shorter (278.4Ϫ287.3 pm).[9] The SbϪP
bond lengths in 1 are in the range 249.4Ϫ252.4 pm and
therefore are similar to the spread of values observed in
[(tmeda)(Me2NH)Na(CyP)4Sb]2 (248.9Ϫ254.1 pm).[10] In
the bicycle [Sb2(PAr)2] (Ar ϭ 2,4,6-tBu3C6H2) mentioned
above these bonds are significantly longer (average value
Herein we report on the synthesis and crystal structures
of the cage and bicyclic compounds [Sb4(PSiMe2Thex)4]
(1), [Sb4(AsSiiPr3)4] (2) and [Sb2(PSiPh2tBu)4] (3), obtained
[a]
Institut für Nanotechnologie, Forschungszentrum Karlsruhe
Postfach 3640, 76021 Karlsruhe, Germany
Fax: ϩ 49-7247-82-6368
E-mail: carsten.vonhaenisch@int.fzk.de
378
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400610
Eur. J. Inorg. Chem. 2005, 378Ϫ382

Novel Binary Compounds of Group 15 Elements
FULL PAPER
257.3 pm).[5b] It is assumed that the longer SbϪP bonds in C6H4(AsMe2)2}] these bonds are significantly longer
the latter compound are due to the large steric requirements (266.4 pm).
of the 2,4,6-tBu3C6H2 substituents. The Sb4P4 motif in 1
can be regarded as being related to the P8 segment in the
structure of Hittorf’s violet phosphorus; an analogous P8R4
compound, however, could not be isolated in a pure
form,[11] whereas a variety of transition metal complexes
with P8 ligands have been described in the literature.[12] The
closest structural relative of 1 is the antimony cage Sb8R4
[R
ϭ CH(SiMe3)2], isolated from the reduction of
RSbCl2with Mg.[9]
Figure 2. Molecular structure of 2; selected bond lengths [pm] and
angles [°]: Sb(1)ϪSb(1Ј) 289.0(2), Sb(2)ϪSb(2Ј) 288.4(2), SbϪAs
260.1(2)Ϫ261.6(2), SiϪAs 239.3Ϫ240.2; Sb(1)ϪAs(1)ϪSb(2)
101.24(5), Sb(1Ј)ϪAs(2)ϪSb(2) 100.69(5), As(1)ϪSb(1)ϪAs(2)
93.72(5), As(1)ϪSb(2)ϪAs(2) 92.09(5), As(1)ϪSb(1)ϪSb(1Ј)
94.94(5), As(2Ј)ϪSb(1)ϪSb(1Ј) 103.96(5), As(1)ϪSb(2)ϪSb(2Ј)
103.99(5), As(2)ϪSb(2)ϪSb(2Ј) 95.46(5)
In the mass spectra of 1 and 2 the molecular ion peaks
at m/z ϭ 1184 and 1416, respectively, as well as the charac-
teristic fragments [Sb4P4(SiMe2Thex)3]ϩ, [Sb3P4Me2-
(SiMe2Thex)3]ϩ and [Sb4As4(SiiPr3)3]ϩ, [Sb4(AsSiiPr3)3]ϩ,
[Sb4As3(SiiPr3)2]ϩ, [Sb2(AsSiiPr3)2]ϩ can be observed.
The novel bicyclic compound 3 was isolated as yellow
crystals from the LiBr elimination reaction of tBuPh2SiPLi2
and SbBr3 in a 3:2 molar ratio. The compound crystallizes
Figure 1. Molecular structure of 1 (inset: side view of the heavy
atom frame); selected bond lengths [pm] and angles [°]: Sb(1)ϪP(1)
249.4(2), Sb(1ЈЈЈ)ϪP(1) 252.4(2), SbϪSb 287.9(1), P(1)ϪSi(1)
228.5(2); Sb(1ЈЈ)ϪSb(1)ϪP(1) 90.42, Sb(1ЈЈ)ϪSb(1)ϪP(1Ј) 104.71,
¯
P(1)ϪSb(1)ϪP(1Ј)
92.97,
Sb(1)ϪP(1)ϪSb(1ЈЈЈ)
102.23,
in the triclinic space group P1. It is composed of five-mem-
Si(1)ϪP(1)ϪSb(1) 105.10, Si(1)ϪP(1)ϪSb(1ЈЈЈ) 106.22
bered P3Sb2 and three-membered PSb2 rings sharing a com-
mon Sb2 bridgehead (Figure 3). Both the P and the Sb
atoms are three-coordinate, with the antimony atoms pos-
The 31P{1H} NMR spectrum of 1 displays, as expected, sessing no exocyclic ligands. The central Sb2P4 unit shows
one singlet at δ ϭ Ϫ104.5 ppm. An additional singlet ap- a non-planar configuration; the plane through Sb(1), Sb(2),
pears at δ ϭ Ϫ65.1 ppm in the 31P{1H} NMR spectrum of P(4) is virtually perpendicular to the Sb2P3 ring. Examin-
the reaction mixture, which presumably can be attributed to ation of the bond lengths and angles found in the bicyclic
significant amounts of (PSiMe2Thex)n (n ϭ 4 or 6), which is Sb2P4 core of 3 indicates that there is a considerable
obtained as a by-product from the reduction process. Un- amount of strain in this arrangement. The fold angles
fortunately, this by-product could not be isolated.
P(1)ϪSb(1)ϪP(4) and P(3)ϪSb(2)ϪP(4) are 86.11° and
[Sb4(AsSiiPr3)4] (2) is obtained from the reaction of 104.3° respectively. The comparatively large difference be-
iPr3SiAsLi2 and SbCl3. It crystallises in the monoclinic tween these angles results from the manner of orientation
space group C2/c with two independent inversion-sym- of the sterically demanding silyl groups coordinated to P(1)
metric molecules in the elementary cell. The molecular and P(3). The tBuPh2Si substituent of P(1) is in a trans
structure of 2 (Figure 2) is almost identical to the phos- position to the Sb(1)ϪP(4) bond, whereas the silyl group
phorus compound 1, but with AsSiiPr3 groups as building bonded to P(3) is in a cis position to the Sb(2)ϪP(4) bond.
blocks instead of the PSiMe2Thex fragments. The SbϪSb The
torsion
angles
Si(3)ϪP(3)ϪSb(2)ϪP(4)
and
bonds in 2 are slightly longer (288.1Ϫ289.0 pm) than those Si(1)ϪP(1)ϪSb(1)ϪP(4) are 46.1° and 135.7° respectively.
in 1. The SbϪAs bonds are in the range 260.1Ϫ261.6 pm, A similar molecular structure occurs in the homonuclear
whereas in the coordination compound [Sb2Cl6{o- bicyclic compound tBu4P6 reported by Baudler and co-wor-
Eur. J. Inorg. Chem. 2005, 378Ϫ382
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
379

D. Nikolova, C. von Hänisch
FULL PAPER
kers.[13] However the arrangement of the tBu groups in this
structure is all-trans. Of particular interest in comparison
of 3 with the other title compounds is the appearance of
PϪP bonds in the structure, resulting from oxidation of the
P atoms and corresponding reduction of the Sb atoms to
SbϪSb bonds. The SbϪSb bond in 3 is 276.8 pm, and is
therefore shorter than the corresponding bonds in 1 and 2.
This bond shortening is possibly a consequence of the fact
that the Sb2 unit is bridged by the P(4) atom. The average
PϪP bond length is 219.6 pm, and the SbϪP bonds are
255.2 pm on average. These values lie in the usual range for
single bonds between these elements.
Figure 4. 31P{1H} NMR spectra of 3 in [D8]toluene: a) at ϩ70 °C,
b) atϪ50 °C
Experimental Section
General: All manipulations were carried out with rigorous ex-
clusion of oxygen and moisture, using a Schlenk line and nitrogen
atmosphere. Solvents were dried and freshly distilled before use.
The starting materials iPr3SiAsH2 and ThexMe2SiPH2 were pre-
pared according to relevant procedures found in the literature.[14]
SbCl3 and SbBr3 were obtained from Aldrich and sublimed before
Figure 3. Molecular structure of 3; selected bond lengths [pm] and
angles [°]: Sb(1)ϪSb(2) 276.8(2), Sb(1)ϪP(1) 255.3(2), Sb(1)ϪP(4)
255.3(2), Sb(2)ϪP(3) 255.9(2), Sb(2)ϪP(4) 254.4(2), P(1)ϪP(2)
219.9(2), P(2)ϪP(3) 219.9(2), P(1)ϪSi(1) 228.7(2), P(2)ϪSi(2)
229.4(2),
P(3)ϪSi(3)
226.9(2),
P(4)ϪSi(4)
227.8(2);
92.63(4),
65.77(6),
112.99(6),
86.11(6),
Sb(1)ϪSb(2)ϪP(4)
Sb(2)ϪSb(1)ϪP(4)
Sb(1)ϪP(1)ϪP(2)
P(1)ϪP(2)ϪP(3)
57.28(5),
56.94(5),
110.71(7),
99.86(8),
Sb(2)ϪSb(1)ϪP(1)
Sb(1)ϪP(4)ϪSb(2)
Sb(2)ϪP(3)ϪP(2)
P(1)ϪSb(1)ϪP(4)
1
use. The H and 31P NMR spectra were recorded on a Bruker AC
250 spectrometer. All isolated compounds gave elemental analyses
consistent with their formulas.
P(3)ϪSb(2)ϪP(4) 104.30(6)
tBuPh2SiPH2: A solution of tBuPh2SiCl (41.2 g, 0.15 mol) in 50
mL of THF was added dropwise to a solution of [(dme)LiPH2]
(19.5 g, 0.15 mol) in 150 mL of THF at 0 °C. After stirring the
mixture overnight at room temperature, the THF was replaced by
100 mL of pentane. The precipitated lithium chloride was sub-
sequently removed by filtration. After removal of the solvent, a
vacuum distillation yielded 20 g (50%) of tBuPh2SiPH2, B.p.:
100Ϫ103 °C (10Ϫ3 mbar). 1H NMR (C6D6): δ ϭ 1.20 [s, 9 H,
The structure of 3 can be deduced from 31P{1H} NMR
spectrum (Figure 4), which shows at room temperature two
triplet signals at δ ϭ Ϫ245 and Ϫ31 ppm for the P(4) and
P(2) centres, respectively. An additional broad signal ap-
pears at δ ϭ Ϫ120 ppm. At ϩ70 °C the signal at δ ϭ
Ϫ120 ppm appears as a doublet of doublets, which is con-
sistent with chemically identical P(1) and P(3) atoms
(AM2X spin system, JP,P ϭ 400, JP,P ϭ 96 Hz). At Ϫ50
°C the 31P{1H} NMR spectrum of 3 shows four multiplets
corresponding to the four different P atoms observed in the
crystal structure (AEMX spin system). The mass spectrum
of 3 does not show the molecular peak, although the
characteristic fragment [(PSitBuPh2)3]ϩ is observed at
m/z ϭ 810.
1
C(CH3)3], 1.73 (d, JP,H ϭ 187 Hz, 2 H, PH2), 7.26 (m, 5 H, Ph),
7.78 (m, 5 H, Ph) ppm. 13C{1H} NMR (C6D6): δ ϭ 19.8 [d, 2JP,C ϭ
21.5 Hz, C(CH3)3], 28.1 [d, 3JP,C ϭ 6.8 Hz, C(CH3)3], 129.9 (s, Ph),
135.7 (d, JP,C ϭ 8.9 Hz, Ph), 136.3 (d, JP,C ϭ 8.9 Hz, Ph). 31P NMR
1
2
1
(C6D6): δ ϭ Ϫ252.2 (t, JP,H ϭ 187 Hz) ppm.
1: n-Butyllithium [1.2 mL (1.92 mmol) of a 1.6 m solution] was
added to a solution of ThexMe2SiPH2 (0.17 g, 0.96 mmol) in 5 mL
of Et2O at 0 °C. After stirring for 10 min, this solution was added
to a solution of SbCl3 (0.15 g, 0.64 mmol) in 15 mL of toluene at
380
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 378Ϫ382

Novel Binary Compounds of Group 15 Elements
FULL PAPER
Table 1. Crystallographic data for 1Ϫ3[7]
1
2
3
Empirical formula
Space group
Formula units
Temperature
C32H76P4Sb4Si4
P42/n
2
C36H84As4Sb4Si4
C2/c
8
C64H76P4Sb2Si4
P1
2
¯
220 K
200 K
200 K
Lattice constants
a ϭ 1881.7(3) pm
b ϭ 1881.7(3) pm
c ϭ 698.8(1) pm
α ϭ 90°
a ϭ 2691.7(5) pm
b ϭ 1620.5(3) pm
c ϭ 2655.6(5) pm
α ϭ 90°
a ϭ 1391.8(3) pm
b ϭ 1414.0(3) pm
c ϭ 2133.2(4) pm
α ϭ 106.25(3)°
β ϭ 92.17(3)°
γ ϭ 118.74(3)°
β ϭ 90°
β ϭ 110.27(3)°
γ ϭ 90°
γ ϭ 90°
3
3
3
˚
˚
˚
Volume
Density
2Θ range
2474.3(7) A
1.589 g/cm3
3Ϫ46°
10866(4) A
1.723 g/cm3
3Ϫ48°
3459.0(12) A
1.272 g/cm3
3.5Ϫ52°
Reflections measured
Independent reflections
Independent reflections with Fo Ͼ 4σ(Fo)
Parameters
µ(Mo-Kα)
R1
3571
15734
12686
9753 (Rint ϭ 0.0525)
7520
1697 (Rint ϭ 0.0304)
1246
7299 (Rint ϭ 0.0476)
5693
100
422
667
2.407 mmϪ1
0.0351
4.496 mmϪ1
0.0598
0.977 mmϪ1
0.0536
wR2 (all data)
Residual electron density
0.0962
0.664 e/A
0.1796
2.539 e/A
0.1565
1.266 e/A
3
3
3
˚
˚
˚
Ϫ70 °C. The reaction mixture was allowed to warm to Ϫ35 °C heptane. After filtration and cooling of the solution to 0 °C yellow
and then kept at the same temperature for an additional 12 h. The
resulting orange solution was filtered to remove the precipitated
crystals of 3 were obtained over a period of 3 d. Yield: 0.20 g (66%).
C64H76P4Sb2Si4 (1325.0): calcd. C 58.01, H 5.78; found C 57.14, H
LiCl and cooled to Ϫ35 °C. Orange crystals of 1 were obtained 6.28. 1H NMR ([D8]toluene): δ ϭ 1.16 (s, 9 H, SitBu), 1.21 (s, 9 H,
over a period of 5 d. Yield: 0.05 g (26%). C32H76P4Sb4Si4 (1184.2):
SitBu), 1.33 (s, 18 H, SitBu), 6.78 (m), 7.19 (m), 7.28 (m), 7.43
1
calcd. C 32.46, H 6.47; found C 32.89, H 6.46. H NMR (C6D6): (m), 7.68 (m), 7.93 (m) (all SiϪPh, 40 H) ppm. 31P{1H) NMR
2
δ ϭ 0.39 (s, 24 H, SiCH3), 1.08 (m, 48 H, overlap of SiCCH3 and
([D8]toluene, 70 °C): δ ϭ Ϫ235.6 (t, JP,P ϭ 96 Hz), Ϫ117.3 (dd,
3
2
1
SiCCCH3), 2.14 [sept, JH,H ϭ 6.9 Hz, 4 H, SiCH(CH3)2] ppm. 1JP,P ϭ 400, JP,P ϭ 96 Hz), Ϫ28.8 (t, JP,P ϭ 400 Hz) ppm. MS
31P{1H} NMR (C6D6): δ ϭ Ϫ104.5 (s) ppm. MS (EI, 70 eV, 200 (EI, 70 eV, 210 °C): m/z (%) ϭ 810 (100) [(PSitBuPh2)3]ϩ, 753 (29)
°C): m/z (%) ϭ 1184 (13) [Mϩ], 1041 (100) [Mϩ Ϫ SiThexMe2], 949
(9.4) [Sb3P4Me2(SiThexMe2)3]ϩ. IR (KBr): ν˜ ϭ 2957 (s), 2867 (m),
1459 (m), 1389 (w), 1376 (m), 1363 (w), 1261 (m), 1241 (s), 1088
[P3(SitBuPh2)2SiPh2]ϩ, 239 (33) [SitBuPh2]ϩ. IR (KBr): ν˜ ϭ 2940
(vs), 2862 (vs), 2097 (w), 1703 (vs, br), 1461 (s), 1379 (m), 1362
(m), 1293 (w), 1227 (m), 1157 (vw), 1068 (m), 1049 (m), 1014 (m),
(m), 1033 (m), 915 (w), 870 (m), 835 (s), 798 (vs), 773 (w), 760 (w), 992 (s), 881 (vs), 700 (vs), 633 (vs), 570 (s), 502 (s), 465 (s), 380
685 (w), 666 (m), 601 (m), 501 (w), 441 (s) cmϪ1 (m) cmϪ1
.
.
2: n-Butyllithium [1.13 mL (1.81 mmol) of a 1.6 m solution] was
added to a solution of iPr3SiAsH2 (0.21 g, 0.9 mmol) in 10 mL of
Et2O at 0 °C. After warming to room temperature, the solution of
iPr3SiAsLi2 was added to a solution of SbCl3 (0.14 g, 0.60 mmol)
in 15 mL of Et2O at Ϫ70 °C. The red mixture was subsequently
warmed to Ϫ35 °C while stirring and kept at the same temperature
overnight. After filtration and cooling of the solution to Ϫ35 °C
red crystals of 2 crystallised over a period of 5 d. Yield: 0.06 g
(29%) C36H84As4Sb4Si4 (1416.1): calcd. C 30.53, H 5.98; found C
31.24, H 6.09. MS (EI, 70 eV, 200 °C): m/z (%) ϭ 1416 (11) [Mϩ],
1259 (36) [Mϩ Ϫ SiiPr3], 1184 (19) [Sb4(AsSiiPr3)3]ϩ, 1027 (23)
[Sb4As3(SiiPr3)2]ϩ, 708 (19) [M/2]ϩ. IR (KBr): ν˜ ϭ 2937 (vs), 2861
(vs), 1457 (s), 1382 (m), 1362 (m), 1288 (w), 1261 (m), 1226 (m),
1068 (m), 1018 (s), 989 (m), 966 (w), 915 (m), 875 (s), 803 (m), 660
X-ray Crystallography: A summary of the crystallographic data for
all three compounds can be found in Table 1 and ref.[7]
Acknowledgments
The authors thank Dr. Dale Cave for his valuable help with the
manuscript and Prof. Dr. D. Fenske for helpful discussions and for
providing excellent working conditions.
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(s), 630 (vs), 588 (m), 555 (s) 499 (vs), 466 (m), 419 (w) cmϪ1
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[2b]
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3: n-Butyllithium [1.15 mL (1.84 mmol) of a 1.6 m solution] was
added to a solution of tBuPh2SiPH2 (0.25 g, 0.92 mmol) in 5 mL
of Et2O at 0 °C. The resulting yellow solution was added dropwise
at Ϫ70 °C to a stirred solution of SbBr3 (0.22 g, 0.61 mmol) in 15
mL of toluene. The purple-red mixture was allowed to warm to
room temperature and stirred for an additional 16 h. The solvent
was removed in vacuo and the residue was dissolved in 5 mL of
[2c]
M. Baudler, P. Bachmann,
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Received July 4, 2004
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382
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