Electrophilic addition of selenium and telluriom halides to methyldiethynylsilane

Article abstract of DOI:10.1134/S1070363209020091

Regio- and stereoselective electrophilic addition reactions of SeCl ₂, SeBr₂, SeCl₄, SeBr₄ to methyldiethynylsilane lead to predominant formation of the Z-isomers of 3,6-dihalo-4-methyl-1,4-selenasilafulvenes, d

Full text of DOI:10.1134/S1070363209020091

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 2, pp. 221–227. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © S.V. Amosova, M.V. Penzik, A.V. Martynov, L.V. Zhilitskaya, M.G. Voronkov, 2009, published in Zhurnal Obshchei Khimii, 2009,
Vol. 79, No. 2, pp. 233–239.
Electrophilic Addition of Selenium and Telluriom Halides
to Methyldiethynylsilane
S. V. Amosova, M. V. Penzik, A. V. Martynov, L. V. Zhilitskaya, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: amosova@irioch.irk.ru
Received June 5, 2008
Abstract―Regio- and stereoselective electrophilic addition reactions of SeCl2, SeBr2, SeCl4, SeBr4 to
methyldiethynylsilane lead to predominant formation of the Z-isomers of 3,6-dihalo-4-methyl-1,4-selenasila-
fulvenes, disiloxanes on their bases, as well as disiloxanes formed upon the reaction with methyldiethynyl-
silane. TeCl4 reacts with methyldiethynylsilane with predominant formation of the E-isomer of 1,1,3,6-
tetrachloro-1-methyl-1-(methyldiethynylsiloxy)-1,4-tellura(IV)silafulvene as a result of the reaction of the
intermediate E-isomer of 4-methyl-1,1,3,6-tetrachloro-1,4-tellura(IV)silafulvene with methyldiethynylsilane.
The structure of the products was proved by the methods of 1H, 77Se NMR, IR spectroscopy and chromatomass
spectrometry.
DOI: 10.1134/S1070363209020091
Addition of Se2Cl2, SCl2 to terminal and internal
alkynes is known to lead to the corresponding bis(2-
chloroalkenyl)diselenides and sulfides by the
mechanism of anti-addition [1–4]. The reaction of
Se2Cl2 with acetylene affords E-2-chloro-1-ethenesele-
nenylchloride due to expulsion of the selenium atom
[5]. Until now, electrophilic reactions of alkynes with
selenium dihalides have not been studied.
Symmetrical 1,4-substituted derivatives of butyne-
diol upon the reaction with TeCl4 give the products of
propargyl rearrangement. Adduct of 1:1 composition
formed in the reaction of TeX4 with 1,4-butynediols is
dehydrated to give disubstituted 2,5-dihydrofurane [19].
Earlier we have reported on the synthesis of selena-
silicon-containing [20–25] and tellurasilicon-contain-
ing unsaturated five-membered heterocycles [26].
They have been obtained by the discovered by us
reactions of electrophilic addition of SeCl2, SeBr2,
SeBr4, SeCl4, and TeCl4 to diorganyldiethynylsilanes.
Before our studies the reactions of selenium dihalides
to alkynes were unknown, and electrophilic addition of
SCl2, SeCl4, and TeCl4 was studied only on the ex-
ample of 4-heterosubstituted hepta-1,6-dienes [27–32].
Prior to our investigations, the electrophilic
addition of selenium tetrahalides SeX4 (X = Br, Cl) to
the triple bond has been described only on the example
of alkynes. Addition of SeCl4 and SeBr4 to acetylene at
low temperatures (from –45 to –78ºC) leads to the Z,Z-
and E,E-bis(2-haloethenyl)selenodihalides [3, 6–9] and
at 20ºC to E,E-bis(2-haloethenyl)selenide [10].
Electrophilic addition of TeX4 (X = Br, Cl) to
acetylene compounds was studied on the example of
only substituted acetylenes: PhC≡CH, PhC≡CPh,
C5H11C≡CH, CH≡CCH2OH [11–19]. The reactions
proceed with the formation of either monoadducts Z-
RCH=CHTeCl3 [11–13, 18, 19] or diadducts
(RXC=CH)2TeX2 [11, 14, 15]. Normally, the syn-addi-
tion takes place although in the case of TeBr4 in
benzene the anti-addition occurs along with the syn-
addition resulting in the mixtures of the Z- and E-
isomers of the corresponding adducts [14, 15].
In continuation of our systematic studies of the
reactions of electrophilic addition of selenium and
tellurium halides to diorganyldiethynylsilanes [20–26]
we have studied electrophilic reactions of SeCl2,
SeBr2, SeCl4, SeBr4, and TeCl4 with methyldiethynyl-
silane (MDES). It was established that the reaction of
1
SeBr2 with MDES, from the data of H NMR, leads
mainly to the mixture of the Z- and E-isomers of 4-
methyl-3,6-dibromo-1,4-selenasilafulvene (Ia) in the
ratio of 5:1 in total yield of 84% (Scheme 1). The Z-
1
isomer is manifested in the H NMR spectrum as the
221

222
AMOSOVA et al.
Scheme 1.
Me
O
Me
H
Si
H
X
Si
Me
X
H
Si
Se
H2O or O2
H
Me
X
H
Me
H
II
H
X
Si
H
Si
+ SeX2
X
Me
Se
Se
I
Si
Me
O
H2O or O2
X
X
H
H
X
Si
H
Se
III
I, II, III: X = Br (a), Cl (b).
signals of the vinyl protons with characteristic for this
isomer long-range coupling constant JHH 1.1 Hz. The
The presence of diethynylsilyl group in molecule IIа is
also confirmed by the IR spectrum which contains the
absorption bands of ethynyl groups.
5
presence of the Si–H bond results in splitting of the
doublet signal of the exocyclic olefinic proton at
7.03 ppm to a doublet of doublets with coupling
1
From the Н NMR data, disiloxane IIIa is formed
4
in 16.5% yield along with 38% of heterofulvene Ia.
GC-MS of disiloxane IIIa shows the corresponding
molecular ion [M]+ 680. The presence of a long-range
constant J(Si)HH 1.2 Hz. In the spectrum of the E-
isomer the endocyclic olefinic proton is displayed as a
singlet at 7.50 ppm), whereas the exocyclic one as a
doublet at 7.21 ppm with the same coupling constant
4J(Si)HH 1.2 Hz. The SiH proton in the spectra of both
isomers shows a characteristic doublet of quartets
(4.86 and 4.94 ppm for the Z- and E-isomers,
respectively). GC–MS of the isomers of heterofulvene
Iа show polyisotopic molecular ions [M]+ 334.
5
coupling JHH 1.1 Hz in the 1H NMR spectrum
between the exo and endocyclic olefinic protons is
indicative of the Z,Z-configuration of disiloxane IVа
[22].
In the reaction of MDES with SeCl2, from the data
1
of GC-MS and H NMR, a mixture of the Z- and E-
isomers of 4-methyl-3,6-dichloro-1,4-selenasilafulvene
A specific feature of the prepared heterofulvenes I
is the presence on their molecules the fragment which
under the conditions of isolation suffers bimolecular
oxidation or co-hydrolysis with MDES to the SiOSi
group, that is, 4-methyl-4-(methyldiethynyl)siloxy-3,6-
dibromo-1,4-selenasila-fulvene (IIа). A similar bi-
molecular reaction of heterofulvene Iа affords
disiloxane framed with two 1,4-selenasilafulvene
groups IIIа (Scheme 1). Compound IIа is formed as
1
Ib (2:1 from H NMR) and Z,Z- and E,E-isomers of
1
disiloxane IIIb (3:2 from H NMR) is formed (Sche-
me 1). 1,4-Selenasilafulvene Ib and disiloxane IIIb in
GC–MS show the corresponding molecular ions [M]+
244 and 502, respectively. The formation of the Z- and
E-isomers of 1,4-selenasilafulvene Ib and Z,Z- and
1
E,E-isomers of disiloxane IIIb is confirmed by the Н
NMR spectrum of the reaction mixture, in which the Z-
5
1
isomers are displayed by a long-range coupling JHH
the Z-isomer as witnessed by the presence in its H
5
1.0–1.2 Hz between the exo and endocyclic olefinic
protons [22]. In the 77Se NMR spectra, these
compounds are characterized by the signals of 77Se in
the range of 488–510 ppm with the doublet of doublets
spin–spin coupling pattern of the 77Se signal and exo
NMR spectrum a long-range coupling JHH 1.1 Hz
between the signals of the exo- and endocyclic olefinic
protons (7.16 and 6.85 ppm). GC–MS of compound
IIа shows a polyisotope molecular ion [M]+ 442, the
content of IIа in the reaction mixture amounts to 10%.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009

ELECTROPHILIC ADDITION OF SELENIUM AND TELLURIOM HALIDES
223
and endocyclic hydrogen atoms, which typical for the
1,4-selenafulvene ring.
NMR spectrum, typical for unsaturated selenasila-
containing cyclopentene heterocycles [22, 33], and the
absence in the H NMR spectrum of the protons of
1
The reaction of SeBr4 with MDES is nonselective
groups ≡СH and SiH suggesting either the formation
of the disiloxane group Si–O–Si binding the two 1,3-
selenasilacyclopentene fragments in the structure of 3-
methyl-3-(2',4'-dichloro-2'-dichloromethyl-3'-methyl-
3'-oxa-1',3'-selenasilacyclopentene-4)-2,4-dichloro-2-
dichloromethyl-1,3-selenasilacyclopentene-4 (Vb), or
chlorination of the Si–H bond with selenium tetra-
chloride with the formation of 2,3,4-trichloro-2-dichloro-
methyl-1,3-selenasilacyclopentene-4 (VIb) (Scheme 2).
1
and from the data of H and 77Se NMR leads to the
mixture of products containing 6% of the Z-isomer of
heterofulvene Ia and 30% of the Z,Z-isomer of
1
disiloxane IIIa (Scheme 2). H and 77Se NMR spectra
of compounds Ia and IIIa are identical to those of the
products formed in the reaction with SeBr2.
The reaction of SeCl4 with DMES practically
quantitatively affords disiloxane IIIb as the Z,Z- and
1
E,E-isomers in the ratio of 5 : 1 from the data of H
1
NMR (Scheme 2). The H NMR spectrum of the Z,Z-
Unlike the reactions of selenium tetrahalides with
MDES, TeCl4 reacts with the latter without reduction
of Te(IV) to Te(II), similar to the reaction of TeCl4
with diorganyldiethynylsilanes [26], and gives rise to
the formation of the Z- and E-isomers of the five-
membered tellurium(IV)silicon-containing heterocycle,
4-methyl-1,1,3,6-tetrachloro-1,4-tellura(IV)silafulvene
VII. However, intermediate VII immediately reacts
isomer of disiloxane IIIb shows characteristic doublet
signals of olefinic protons with long-range coupling
5JHH 0.7 Hz, whereas its E,E-isomer shows only singlet
signals of the exo- and endocyclic protons (7.34 and
6.78 ppm). The GC-MS of disiloxane IIIb shows
polyisotopic molecular ion [M]+ 502. From the data of
1H and 77Se NMR, the reaction mixture contains 10%
of unidentified compound, probably, chloroderivative
VIb of 3-methyl-2,6-dichloro-2-dichloromethyl-1,3-
selenasilacyclopentene-4 (IVb). This is indicated by
the presence of a doublet signal at δ 652 ppm with the
1
with MDES leading, from the data of H NMR, to the
formation of the Z- and E-isomers of 1,1,3,6-
tetrachloro-1-methyl-1-(methyldiethynylsiloxy)-1,4-
tellura(IV)sila-fulvene VIII in 36% yield and with the
ratio Z : E = 1 : 5 (Scheme 3).
2
geminal coupling constant JSeH 50 Hz in the 77Se
Scheme 2.
H
H
Me
X
X
H
H
X
Si
Se
Se
H2O or O2
O
Me
Si
X
H
H
Si
Se
X
H
X
Ia, Ib
IIIa, IIIb
H
Me
H
X
CHCl3
Si
+ SeX4
Se
CHX2
O
Me
Si
X
Si
Se
X
X
H2Oor O2
H
Me
CHX2
Vb
H
X
Si
X
Me
H
CHX2
Se
X
H
H
Si
X
SeX4
IVb
CHX2
Se
VIb
I, III, IV, V, VI: X = Br (a), Cl (b).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009

224
AMOSOVA et al.
Scheme 3.
H
Si
H
Me
Si
Me
O
Cl
Me
H
Si
Cl
H
20oC, CHCl3
Si
+ TeCl4
Me
TeCl4, O2 or H2O
Te
Cl
Me
H
Cl
Si
Te
Cl
Cl
H
H
Cl
VIII
Cl
VII
Tetracoordination of tellurium atom in heterocycle
VIII was proved by the method of 125Te NMR
showing the signal at δ 855 ppm which is indicative of
a tetracoordinated tellurium atom [34–36]). The
doublet signal of tellurium is characterized by geminal
coupling constant 2JTe–H 118 Hz, and a similar coupling
of the satellite signals of the olefinic protons is
observed in the 1H NMR spectrum. Since, according to
calculations, the coupling constants between tellurium-
125 and proton are approximately twice as large as the
corresponding constants for selenium-77 [37], the
experimentally obtained geminal constants 2JTe–H are in
good agreement with the values of the geminal
containing heterocycles [20–22, 24–26, 38]. From the
data of elemental analysis, the ratio Te : Cl = 1 : 4, that
proves the composition of heterocycle VIII.
Formation of heterofulvenes Ia and Ib and their
derivatives IIа, IIIa, and IIIb in the reaction of MDES
with selenium tetrahalides is, apparently, due to
concurrent reduction of selenium tetrahalides by
methyldiethynylsilane to selenium dihalides which
enter further reactions. Since in the starting MDES the
Si–H bond is rather stable as proved by its stability
upon storage at 0ºС, the formation of the disiloxane
bond in heterofulvenes Iа and Ib is, probably, due to
enhanced accessibility of the hydrogen atom at the
silicon atom in the heterocycle.
2
constants JSe–H of 50–60 Hz found by us earlier [20–
23], as well as with those for compounds I–VI
described above. The Z- and E-isomers of heterocycle
VIII were identified by the presence of a long-range
Formation of heterocycle VII and its further
transformation into product VIII can be explained by
successive electrophilic addition of TeCl4 to two
acetylenic fragments of MDES (Scheme 4). Since the
reaction results mainly in the E-isomer VII it can be
assumed that on the first stage the anti-Markovnikov
anti-addition occurs with subsequent cycloaddition of
the intermediate telluriumtrichloride A to the second
ethynyl fragment of MDES. Appearance of the Z-
isomer of VII leading to the Z-isomer of VIII is,
apparently, due to post-isomerization of the inter-
mediate monoadduct of the anti-addition А into the
monoadduct of the formal syn-addition B which can be
5
coupling constant JHH 0.7 Hz between the exo- and
endocyclic olefinic protons in the Z-isomer, lacking in
the predominant E-isomer. As was shown by us earlier
[20–26] and demonstrated above, the presence of such
a coupling is a clear evidence of the formation of the
Z-isomers of the five-membered unsaturated chalco-
genosilicon-containing heterocycles of fulvene structure.
In the mass spectrum of heterocycle VIII only the
ions of fragmentation appear [M – Cl2]+, that is typical
for the five-membered unsaturated chalcogenosilicon-
Scheme 4.
R1
R
R1
R
Cl
R1
H
R1
R
Si
Si
Si
Si
TeCl2
+ TeCl4
TeCl3
H
TeCl3
Cl
R
Cl
H
Cl
H
A
B
VII
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ELECTROPHILIC ADDITION OF SELENIUM AND TELLURIOM HALIDES
225
stabilized by intramolecular interaction of the chlorine
atom at the double bond with the tellurium atom of the
TeCl3 group.
Compound Z-IIа. IR spectrum, ν, cm–1: 1068 (Si–
O–Si), 2042, 2154 (С≡С), 3276 (≡СH). Н NMR, δ,
1
ppm: 0.44 s, 0.47 s (CH3–Si, CH3–Si–O–), 2.53 s, 2.54
s (≡CH), 7.21 d (1H, =CHBr, 5JHH 1.1 Hz), 7.58 d (1H,
EXPERIMENTAL
5
SeCH=, JHH 1.1 Hz). 77Se NMR, δ, ppm: 576.8 d.d
1H (400.1 MHz), 77Se (76.30 MHz), and 125Te
(126.4 MHz) NMR spectra were registered on a
Bruker DPX-400 spectrometer in 5–10% solutions in
CDCl3 of acetone-d6 with HMDS as an internal
standard; 125Te NMR spectra were obtained with
respect to Me4Te. Chromatomass spectra were taken
on a Shimadzu QP5050A spectrometer, electron
impact, 70 eV, capillar column SPB-5ms, 60 m,
injector temperature 260°C, column temperature 70–
260°C. IR spectra were taken on a Bruker IPS 25
spectrometer in thin layer and vaseline oil.
Methyldiethynylsilane I was prepared by the known
procedure [39].
(2JSe–H 53.3 3JSe–H 9.4 Hz). Mass spectrum, m/z (Irel., %)
(80Se, 28Si, 79Br): 442 (16.4) [M+]; 361 (6.2), 347 (5.2),
335 (8.16), 311 (26), 297 (4.4), 261 (15.4), 233 (70.8),
231 (66.2), 207 (10.1), 193 (7.3), 177 (18.2), 147 (13),
115 (8.6), 93 (74), 83 (44), 67 (15.5), 53 (100), 43
(24).
Similarly, to 1.10 g of SeBr2 prepared as above, in
10 ml of CHCl3 in the atmosphere of dry oxygen-free
argon 0.40 g of MDES in 15 ml of CHCl3 was added
dropwise at –5ºС, after 14 h of stirring 0.84 g of the
1
mixture was obtained containing, from the data of H
NMR, 65% of heterofulvene Ia as the Z-isomer (yield
39%), and 35% of Z,Z-4-methyl-4-(3',6'-dibromo-4'-
methyl-4'-oxa-1,4-selena-silafulvene)-3,6-dibromo-1,4-
selenasilafulvene IIIa (yield 10%).
Reaction with selenium dibromide. To the
solution of 1.10 g of SeBr2 in 10 ml of CHCl3,
prepared from 0.36 g of powdered selenium and 0.74 g
of bromine, in argon atmosphere at –5°C was slowly
added 0.43 g of MDES (containing 15% of hardly
separable admixture of Et2O) in 15 ml of CHCl3. The
reaction mixture was allowed to reach room
temperature and stirred for 24 h. The precipitate was
filtered off, the solvent removed in vacuum to obtain
1.52 g of the mixture containing, from the data of GC–
MS and multinuclear NMR spectroscopy, the Z- and
E-4-methyl-3,6-dibromo-1,4-selenasilafulvenes Ia and
Z-4-methyl-4-methyldiethynylsiloxy-3,6-dibromo-1,4-
Compound Z,Z-IIIa. 1Н NMR, δ, ppm: 0.57 s (3H,
CH3–Si), 0.88 s (3H, CH3–Si), 7.28 d ]1H, =CHBr,
3
3
5JHH 1.1, JSe–H 12.4, JSi–H(cis) 5.4 Hz], 7.62 d [1H,
=CHSe, JHH 1.1, JSe–H 53.7, JSi–H(trans) 12.6 Hz]. 77Se
5
2
3
NMR, δ, ppm: 555.7 d.d (2JSe–H 53.3, JSe–H 12.5 Hz).
3
IR spectrum, ν, cm–1: 1091 (Si–O–Si), 1555 s (C=C),
2850-3041 (СН3). Mass spectrum, m/z (Irel, %) (80Se,
28Si, 79Br): 680 (11.5) [M+]; 601 (31.3) [M – Br]; 520
(13.3), 441 (11.5), 417 (6.5), 363 (19.5), 341 (32.7),
287 (95.6), 261 (24.5), 231 (37.7), 207 (23.2), 183
(20.2), 147 (32.3), 137 (15.8), 107 (26.5), 93 (86), 83
(78.5), 53 (100), 43 (53).
1
selenasilafulvene IIа. From the data of H NMR, the
ratio Z-Ia : E-Ia : Z-IIа is 67 : 9 : 15. The calculated
Reaction with selenium dichloride. To the
solution of 0.62 g of selenium dichloride prepared in
24 h from 0.33 g of fine-powdered selenium and 0.56 g
of SO2Cl2 in 10 ml of CHCl3 40 g of MDES,
containing Et2O as an admixture, in 15 ml of CHCl3
was slowly added at –5ºС in argon atmosphere, the
obtained reaction mixture stirred for 24 h, then kept in
the solution for 5 days. The precipitate was filtered off,
solvent removed in vacuum to afford 0.77 g of the
mixture containing, from the data of GC-MS, 57% of
4-methyl-3,6-dichloro-1,4-selenasilafulvene Ib (yield
43%) and 33.5% of Z,Z- and E,E-3,6-dichloro-4-
methyl-4-(3',6'-dichloro-4'-methyl-4'-oxa-1',4'-selena-
silafulvene)-1,4-selenasila-fulvene IIIb in the ratio of
2 : 1 from the data of 1H NMR.
yield of heterofulvene Ia is 75%.
1
Compound Ia. H NMR, δ, ppm, for Z-isomer:
0.46 d (3H, CH3–Si, 3JHH 3.7 Hz), 4.86 d q (1H, Si–H,
4
5
3JHH 3.7, J(Si)H–H 1.3 Hz), 7.03 d d (1H, =CHBr, JHH
3
4
3
1.1, J(Si)H–H 6.7, J(Si)H–H 1.2, JSeH 13.4 Hz), 7.53 d
5
2
(1H, SeCH=, JHH 1.1, JSe–H 54.5 Hz); for E-isomer:
0.55 d (3H, CH3–Si, J(Si)H–H 3.7 Hz), 4.94 d.q (1H,
Si–H, J(Si)H–H 3.6 Hz, J(Si)H–H 1.6 Hz), 7.16 d (1H,
3
3
4
4
2
=CHBr, J(Si)H–H 1.1 Hz), 7.50 с (1H, SeCH=, JSe–H
55.3 Hz). 77Se NMR, δ, ppm, for Z-isomer: 571.4 d.d
(2JSe–H 54.3, JSe–H 13.6 Hz); for E-isomer: 534.9 d.d
3
(2JSe–H 53.3, JSe–H 13.5 Hz). GC–MS, m/z (Irel., %)
3
(80Se, 28Si, 79Br): 2 peaks, 334 (24.5) [M+]; 319 (5.6)
[M – CH3]+; 293 (3.4), 253 (10.4) [M – Br]+; 229
(26.3) [M – C2Br]+; 203 (59.6), 147 (28.2), 123 (17.0),
109 (17.1), 93 (6.7), 77 (11.6), 69 (38), 67 (12.1), 53
(100), 43 (58.2).
1
Compound Z- and E-Ib. Н NMR, δ, ppm: 4.99 q
(1H, Si–H, 3JHH 3.6 Hz) 4.90 q (1H, Si–H, 3JHH 3.3 Hz),
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AMOSOVA et al.
1
in the range δ 7.5–6.6 ppm a groups of signals of
similar intensity is observed from which it is
impossible to separate the signals belonging to
compound Ib. GC–MS, m/z (Irel, %) (80Se, 28Si, 35Cl): 2
peaks, 244 (24.9) [M+]; 229 (7.9) [M – CH3]+; 158
(12.2) , 141 (16), 139 (29), 113 (93), 105 (19), 97 (20),
79 (19.5), 63 (50.4), 53 (49.5), 44 (100).
(2JSeH 50.2 Hz). H, 77Se NMR and GC–MS of com-
pounds Z,Z- and E,E-IIIb see above.
Reaction with tellurium tetrachloride. 1.42 g
TeCl4 and 0.50 g MDES were stirred in argon
atmosphere in 35 ml CHCl3 for 8 h at room tem-
perature. The precipitate of dark tarry substance
formed (Te and unreacted TeCl4) was filtered off.
After removal of solvent in vacuum 0.45 g (36%) of
the mixture of the Z- and E-isomers of 4-methyl-4-
methyldiethynylsiloxy-1,1,3,6-tetrachloro-1,4-tellura(IV)-
silafulvene VIII was obtained (the ratio Z : E = 1 : 5,
from the data of 1H NMR) as a yellow-brown powder,
mp 80–85ºС.
Compound IIIb. IR spectrum, ν, cm–1: 1070 (Si–
1
O–Si), 2042, 2162 (C≡C), 3281 (≡СH). Н NMR, δ,
ppm, for Z,Z-isomer: 0.76 s (3H, CH3–Si), 6.96 d (1H,
3
5
2
5JHH 0.7, JSe–H 9.2 Hz), 7.37 d (1H, JHH 0.7, JSe–H
52.9 Hz); for E,E-isomer: 0.90 s (3H, CH3–Si), 6.79 s
3
2
(1H, JSe–H 8.7 Hz), 7.33 s (1H, JSe–H 54.2 Hz). 77Se
NMR, δ, ppm, for Z,Z-isomer: 488.6 d.d (2JSe–H 53.3,
3JSe–H 10.4 Hz); for E,E-isomer: 503.4 d.d (2JSe–H 54.3,
3JSe–H 8.2 Hz). GC-MS, m/z (Irel, %) (80Se, 28Si, 35Cl):
2 peaks, 502 (9.6) [M+]; 243 (6.3), 219 (8.2), 207
(37.6), 197 (33.2), 187 (9), 157 (7.7), 115 (15.8), 93
(19.4), 83 (11.6), 65 (9.1), 53 (17.1), 44 (100), 36 (27).
Compound VIII. 1Н NMR, δ, ppm (acetone-d6) for
the E-isomer: 0.64 s (6H, CH3), 2.07 s (2H, ≡CH,
coincides with the signal of acetone-d6), 8.07 s (1H,
3JTe–H 14.4 Hz), 8.30 s (1H, JTe–H 123, JTe–H 10 Hz);
for the Z-isomer: 0.58 s (6H, CH3), 2.07 s (2H, ≡CH,
coincides with the signal of acetone-d6), 7.69 d (1H,
2
3
5JHH 0.7 Hz), 8.34 d (1H, JHH 0.7, JTe–H 133 Hz).
125Te NMR, δ, ppm (acetone-d6, from Me4Te) for the
E-isomer: 854.7 d (2JTe–H 139.9 Hz). GC–MS, m/z (Irel,
%) (130Te, 35Cl, 28Si): 2 peaks, 402 (20.4) [M – Cl2]+;
335 (3.1), 290 (3.5), 247 (19.7), 237 (6.0), 221 (11.7),
207 (15.0), 197 (57.1), 187 (100), 157 (10.4), 137
(16.0), 115 (14.6), 93 (67.9), 83 (40.5), 63 (27.4), 53
(77.6), 43 (26.7), 36 (66.9). Found, %: C 25.43, H
2.45, Cl 29.55, Si 11.68, Te 26.88. C10H10Cl4Si2TeO.
Calculated, %: C 25.46, H 2.14, Cl 30.06, Si 11.91, Te
27.05.
5
2
Reaction with selenium tetrabromide. Mixture of
1.39 g SeBr4 prepared in situ from 0.27 g of fine
dispersed selenium and 1.12 g Br2, and 0.33 g MDES
in 45 ml of chloroform were stirred in argon
atmosphere at room temperature for 24 h. After
removing of solvent in vacuum 1.52 g of the mixture
of products was obtained as black viscous liquid
containing, from the data of 1Н NMR, Z-4-methyl-3,6-
dibromo-1,4-selenasilafulvene Ia (6% from the data of
1H NMR) and Z,Z-4-methyl-4-(3',6'-dibromo-4'-methyl-
4'-oxa-1,4-selenasilafulvene)-3,6-dibromo-1,4-selenasila-
fulvene IIIa (30% from the data of 1Н NMR). 1H, 77Se
NMR and mass spectra of compounds Z-Ia and Z,Z-
IIIa see above.
ACKNOWLEDGMENTS
This work was financially supported by the
Presidium of Russian Academy of Sciences (project
no. 8.19).
Reaction with selenium tetrachloride. 1.17 g
SeCl4 (Aldrich) and 0.50 g MDES containing Et2O as
an admixture was stirred in 30 ml of chloroform in
argon atmosphere at room temperature for 4 h and
allowed to stay overnight. The precipitate was filtered
off and after removal of the solvent in vacuum 1.54 g
(100% yield) of the mixture of the Z,Z- and E,E-
isomers of 4-methyl-4-(3',6'-dichloro-4'-methyl-4'-oxa-
1',4'-selenasilafulvene)-3,6-dichloro-1,4-selenasilafulvene
IIIb in the ratio of 5 : 1 was obtained, containing 10%
of unidentified product, possibly, 3-methyl-3-(2',4'-
dichloro-2'-dichloromethyl-3'-methyl-3'-oxa-1',3'-selena-
silacyclopentene-4)-2,4-dichloro-2-dichloromethyl-1,3-
selenasilacyclopentene-4 Vb or 3-methyl-2-dichloro-
methyl-2,3,4-trichloro-1,3-selenasilacyclopentene-4 VIb.
1Н NMR, δ, ppm: 0.94 s (3H, CH3–Si), 6.54 s (1H,
CHCl2), 7.41 s (1H, =CH). 77Se NMR, δ, ppm: 651.5 d
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