Reactions of a highly crowded triorganotin iodide with silver salts. Migration of a methyl group from silicon to tin within a cation

Ashrafolmolouk Asadi, Anthony G. Avent, Colin Eaborn, Michael S. Hill, Peter B. Hitchcock, Margaret M. Meehan, J. David Smith

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Abstract

Reaction of the highly crowded organotin iodide CH2Me2Si(Me3Si)2CSnMeIC(SiMe3 )2SiMe2CH2 with AgBF4 gives the fluoride CH2Me2Si(Me3Si)2CSnMeFC(SiMe3 )2SiMe2CH2. Reaction with AgOSO2C6H4Me followed by workup in moist air gives the hydroxide CH2-Me2Si(Me3Si)2CSnMe(OH)C(SiMe 3)2SiMe2CH22, 2f. With AgOSO2CF3 the product is the organosilicon trifluoromethanesulfonate CH2Me2Si(Me3Si)2CSnMe2C(S iMe3)(SiMe2OSO2CF3)-SiMe2 CH2, 5, formed apparently by an unprecedented 1,3-migration of a methyl group from silicon to tin within a cation. Compound 5 and Ph3SiOSC2CF3 are the first silicon trifluoromethanesulfonates to be characterized by X-ray structure determinations. In both the Si-O bonds are long, ca. 1.75 Å, consistent with the ready nucleophilic displacement of [OSC2CF3]- from silicon centers. The crystal structures of the fluoride CH2Me2Si(Me3Si)2CSn-(CH2P h)FC(SiMe3)2SiMe2CH2 and the hydroxide 2f have also been determined.

Original languageEnglish
Pages (from-to)2183-2188
Number of pages6
JournalOrganometallics
Volume21
Issue number11
DOIs
Publication statusPublished - 27 May 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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