Facile Skeletal Rearrangement of Polycyclic Disilenes with Bicyclo[1.1.1]pentasilanyl Groups.
Chemistry
; 24(44): 11393-11401, 2018 Aug 06.
Article
em En
| MEDLINE
| ID: mdl-29806095
ABSTRACT
The unexpected formations of fused polycyclic disilenes 2 a and (E),(Z)-3 b by the reduction of the 1,2-dibromodisilanes 5 a (R=Me) and 5 b (R=iPr) bearing bicyclo[1.1.1]pentasilanyl (BPS) groups is reported. The disilenes 2 a and (E),(Z)-3 b were characterized by a combination of NMR spectroscopy and X-ray diffraction analysis (XRD). The reduction of 5 b in the presence of 2,3-dimethyl-1,3-butadiene provided an ene adduct of the disilene 1 b bearing BPS groups, which suggested that an initial product of the reduction of 5 b was the disilene 1 b. Thermal reactions of 2 a and (E),(Z)-3 b afforded the highly strained saturated silicon clusters 4 a and 4 b. A computational study suggested that the transformation of 1 to 2, 3, or 4 can involve silyldisilene-disilanylsilylene rearrangement reactions and insertion reactions of a silylene into a Si-Si bond.
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MEDLINE
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En
Ano de publicação:
2018
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Article