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932
935
622
1128
778
705
1717
1016
1337
524
871
1460
1075
g-C4H6
(b)
658.0
SiCl4
896.4
g-C4H6
754.1
1632.0
577.6
845.9
1179.9 1064.3
C4H6
1
1
886.7
1
1
1
1172.7 C4H6
1
698.9 1
982.7
1
1800
1600
1400
1200
n/cm–1
1000
800
600
Figure 2 (a) The M06-2X/6-311++G(d,p) calculated spectrum of cis-2 and
(b) experimental difference IR spectrum of a matrix with SiCl2 :C4H6 :Ar =
= 2:7:1000 after photolysis at l > 280 nm for 15 min and after subsequent
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trans-C4H6 and SiCl4 are marked with symbols 1, , g-C4H6, C4H6 and
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In addition to compounds 1 and 2, the formation of some minor
yet unidentified products stable to any used light occurred upon
phototransformations of the complex. Their appearance indicates
the overall complexity of photochemical behavior of the studied
system. The formation of only the same additional products, but
in larger amounts, also accompanied rearrangement of 2 into 1
caused by unfiltered light. Thus, the reactions occurring during the
phototransformations of the complex and compound 2 are the
same. This allows one to suppose that the rearrangement of 2
into 1 proceeds mostly via an initial decomposition of 2 into
starting reactants (into the complex), rather than directly.
In conclusion, the photoinduced transformation of the complex
between butadiene and SiCl2 caused by the light of l > 280 nm
was estimated as providing 1,1-dichloro-2-vinylsilirane 2 and
1,1-dichloro-1-silacyclopent-3-ene 1 in a ratio of ~3:2 on the
basis of integral intensities of bands of 1 and 2, and their
changes in the course of the isomerization of 2 into 1 (Figure S8,
Online Supplementary Materials). Thus, in contrast to the thermal
reaction between SiCl2 and C4H6, wherein 2 can be formed only
as a minor product (vide supra), the photoinduced reaction
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This work was supported by the Russian Science Foundation
(grant no. 14-13-01456).
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2018.11.002.
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Received: 27th June 2018; Com. 18/5621
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