Synthesis and Structural Studies on Dimeric Organotin Cations

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• 作者：Katsumasa Sakamoto ; Hiroshi Ikeda ; Haruo Akashi ; Takahide Fukuyama ; Akihiro Orita ; and Junzo Otera
• 刊名：Organometallics
• 出版年：2000
• 出版时间：August 7, 2000
• 年：2000
• 卷：19
• 期：16
• 页码：3242 - 3248
• 全文大小：141K
• 年卷期：v.19,no.16(August 7, 2000)
• ISSN：1520-6041

文摘

Novel dimeric organotin cations [R₂SnOH(OTf)(H₂O)]₂ (R = n-Bu, t-Bu, and 2-phenylbutyl;Tf = CF₃SO₂) were synthesized from R₂SnO and TfOH. The structures of these compoundswere investigated by single-crystal X-ray analysis and solid-state ¹¹⁹Sn NMR in the solidstate and ¹¹⁹Sn NMR spectra together with electrical conductivity measurements in solution.tert-Butyltin and 2-phenylbutyltin derivatives have cationic structures both in the solid stateand in solution. The n-butyltin derivative is nonionic in the solid state but dissociates intoionic species in solution. The H₂O molecule in this compound can be readily replaced byhexamethylphosphoric triamide (HMPA); the resulting adduct has a similar structure. Thecorresponding nitrate has a nonionic dimeric structure with bidentate nitrate coordination,[t-Bu₂SnOH(NO₃)]₂. As such, it is concluded that both bulky alkyl groups attached on tinand electronegative ligands such as triflate are crucial for generation of the cationic species.