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

被引：10

作者：

Asadi, A ^{[1
]}

Avent, AG ^{[1
]}

Eaborn, C ^{[1
]}

Hill, MS ^{[1
]}

Hitchcock, PB ^{[1
]}

Meehan, MM ^{[1
]}

Smith, JD ^{[1
]}

机构：

[1] Univ Sussex, Sch Chem PHys & Environm Sci, Brighton BN1 9QJ, E Sussex, England

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 11期

关键词：

D O I：

10.1021/om011079z

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of the highly crowded organotin iodide CH2Me2Si(Me3Si)(2)CSnMeIC(SiMe3)(2)SiMe2CH2 with AgBF4 gives the fluoride CH2Me2Si(Me3Si)(2)CSnMeFC(SiMe3)(2)SiMe2CH2. Reaction with AgOSO2C6H4Me followed by workup in moist air gives the hydroxide CH2Me2Si(Me3Si)(2)CSnMe(OH)C(SiMe3)(2)SiMe2CH2, 2f. With AgOSO2CF3 the product is the organosilicon trifluoromethanesulfonate CH2Me2Si(Me3Si)(2)CSnMe2C(SiMe3)(SiMe2OSO2CF3)SiMe2CH2, 5, formed apparently by an unprecedented 1,3-migration of a methyl group from silicon to tin within a cation. Compound 5 and Ph3SiOSO2CF3 are the first silicon trifluoromethanesulfonates to be characterized by X-ray structure determinations. In both the Si-O bonds are long, ca. 1.75Angstrom, consistent with the ready nucleophilic displacement of [OSO2CF3](-) from silicon centers. The crystal structures of the fluoride CH2Me2Si(Me3Si)(2)CSn(CH2Ph)FC(SiMe3)(2)SiMe2CH2 and the hydroxide 2f have also been determined.

引用

页码：2183 / 2188

页数：6

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