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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 15, Number 1
BKCSDE 15(1)
January 20, 1994 

 
Title
Photochemistry of Tris (trimethylsilyl)methylsilane
Author
Seung Ki Hong, Bong Hyun Boo*, Hee Jang Rhee, Sung Kwon Kang, Jae Ryong Kim, Young-Woo Kwak
Keywords
Abstract
UV photolyses of the titled polysilane, MeSi(SiMe3)3 (Ⅰ) in the presence or absence of trapping agents of 2-methyl-1,3-butadiene, methanol (CH30H, CH3OD) and HSi(C2H5)3 have been performed to investigate fragmentation patterns of permethylated oligosilanes. After photolysis, I behaves in three different chemical reactivities: 1,1-elimination yielding Me-Si-SiMe3 (Ⅱ) and its counterpart, Me3SiSiMe3 as the major pathway, and several minor pathways involving 1,1-elimination giving rise to (Me3Si)2SiMe2+:SiMe2 and direct homolytic cleavage giving rise to Me3Si·+·SiMe(SiMe3)2(Ⅲ ). The intermediacy of :SiMe2, Ⅱ and Ⅲ are evidenced by the trapping experiments in which the silylenes and silyl radical saturate their valencies to form the corresponding stable products via incorporation and H(D)-acquisition, respectively. The PM3 semiempirical calculation has permitted the elucidation of the energetics of the various reactions.
Page
68 - 74
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