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

doi:10.1021/om011079z

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

University of Sussex

Research output: Contribution to journal › Article › peer-review

12 Citations (SciVal)

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 language	English
Pages (from-to)	2183-2188
Number of pages	6
Journal	Organometallics
Volume	21
Issue number	11
DOIs	https://doi.org/10.1021/om011079z
Publication status	Published - 27 May 2002

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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

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 {\AA}, 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.",

author = "Ashrafolmolouk Asadi and Avent, {Anthony G.} and Colin Eaborn and Hill, {Michael S.} and Hitchcock, {Peter B.} and Meehan, {Margaret M.} and Smith, {J. David}",

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AU - Asadi, Ashrafolmolouk

AU - Avent, Anthony G.

AU - Eaborn, Colin

AU - Hill, Michael S.

AU - Hitchcock, Peter B.

AU - Meehan, Margaret M.

AU - Smith, J. David

PY - 2002/5/27

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N2 - 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.

AB - 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.

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

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