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Dimerization of a lattice-framework silanone into the corresponding 1,3-dioxa-2,4-disiletanes
Authors:Shinobu Tsutsui  Hiromasa Tanaka  Shigeki Matsumoto
Affiliation:a Photodynamics Research Center, RIKEN (The Institute of Physical and Chemical Research), 519-1399 Aoba, Aramaki, Aoba-ku, Miyagi, Sendai 980-0845, Japan
b Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan
Abstract:A lattice-framework silanone, a racemate of (4R,6R)- and (4S,6S)-2,3,4,6,7,8-hexa-tert-butyl-1,5-disilatricyclo[4.2.0.01,4]octa-2,7-dien-5-one (4), was generated by the photoreaction of the corresponding lattice-framework disilene, a racemate of (4R,6R,4′R,6′R)- and (4S,6S,4′S,6′S)-2,3,4,6,7,8,2′,3′,4′,6′,7′,8′-dodeca-tert-butyl-[5,5′]bi{1,5-disilatricyclo[4.2.0.01,4]octylidene}-2,7,2′,7′-tetraene (dl-1), with mesitonitrile oxide. The silanone 4 was dimerized to produce a mixture of the corresponding dl- and meso-1,3-dioxa-2,4-disiletane derivatives 2. DFT calculations suggested that the non-selective dimerization of 4 to 2 is attributed to the irreversibility of the reaction.
Keywords:Organosilicon compound   1,3-Dioxa-2,4-disiletane   Silanone   Density functional theory
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