Pentamethyldisilyl radical: Absolute rate constants for its formation and for some halogen abstraction and addition reactions

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DOIResolve DOI: http://doi.org/10.1021/jo00363a010
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TypeArticle
Journal titleJournal of Organic Chemistry
ISSN0022-3263
Volume51
Issue13
Pages24572460; # of pages: 4
AbstractPentamethyldisilane is a better hydrogen donor than Et 3SiH toward tert-butoxyl (k's for the overall reaction are 17 and 5.7 × 10 6 M -1 s -1, respectively, at ca. 27°C) and toward primary alkyl radicals (k's for Si-H bond cleavage are ca. 10 and 1.0 × 10 4 M -1 s -1, respectively, at 120°C). Absolute rate constants for various reactions of the Me 3SiSiMe 2·radical have been measured by laser flash photolysis at room temperature. In halogen atom abstractions, for example, the Me 3SiSiMe 2·radical is slightly less reactive than Et 3Si·, but it is more reactive than n-Bu 3Ge· and n-Bu 3Sn·. Pentamethyldisilane would appear to offer an attractive alternative to n-Bu 3SnH and n-Bu 3GeH in radical chain reactions in which the desired product is formed by a hydrogen transfer not to the organic radical formed initially but to a second radical formed by a slow β-scission or rearrangement of the initial radical.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276586
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Record identifierdc8e7255-2e79-46b8-b8ac-334e256cb153
Record created2015-10-13
Record modified2016-05-09
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