Add time:09/03/2019         Source:sciencedirect.com

Photolysis of heptamethyl-2-phenyltrisilane and of octamethyl-2,3-diphenyltetrasilane in the presence of dimethyl sulfoxide (DMSO) occurs by two major pathways. The first involves loss of methylphenylsilylene, which reacts with DMSO to yield methylphenylsilanone and dimethyl sulfide. Methylphenylsilanone has been trapped by reaction with hexamethylcyclotrisiloxane (VII) to yield heptamethylphenylcyclotetrasiloxane and by 1,1,3,3-tetramethyl-2-oxa-1,3-disilacyclopentane (XIII) to yield 1,1,3,5,5-pentamethyl-3-phenyl-2,4-dioxo-1,3,5-trisilacycloheptane. The second pathway involves nucleophilic attack by the oxygen of DMSO on a phenyl substituted silicon atom leading to migration of a phenyl group to an adjacent silicon atom with formation of methyl(trimethylsilyl)silanone and dimethyl sulfide. Methyl(trimethylsilyl)silanone has been trapped by reaction with VII to yield heptamethyl(trimethylsilyl)cyclotetrasiloxane and by XIII to yield 1,1,3,5,5-pentamethyl-3-trimethylsilyl-2,4-dioxa-1,3,5-trisilacycloheptane. Possible mechanisms for these reactions are considered.

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