有机锡骨架上 Sn-C 和 S-C(烷基)键的断裂：一种新型含甲基锡和二甲基锡片段的有机锡-亚硫酸盐簇的合成与表征。

Cleavage of Sn-C and S-C(alkyl) bonds on an organotin scaffold: synthesis and characterization of a novel organotin-sulfite cluster bearing methyltin- and dimethyltin fragments.

机构信息

Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi, 110016, India.

出版信息

Inorg Chem. 2010 May 17;49(10):4708-15. doi: 10.1021/ic100465u.

PMID:20405960

Abstract

Hydrolysis of the mixed-ligand dimethyltin(ethoxy)ethanesulfonate, Me(2)Sn(OEt)(OSO(2)Et) (1a) in moist hexane proceeds via disproportionation and partial cleavage of Sn-C and S-C bonds to afford a novel oxo-/hydroxo- organotin cluster of the composition [(Me(2)Sn)(MeSn)(4)(OSO(2)Et)(2)(OH)(4)(O)(2)(SO(3))(2)] (1) bearing both mono- and dimethyltin fragments and in situ generated sulfite (SO(3)(2-)) anion in the structural framework. On the other hand, similar reactions with analogous mixed ligand diorganotin precursors, R(2)Sn(OR(1))(OSO(2)R(1)) (R = n-Bu, R(1) = Et (2a); R = Et, R(1) = Me (3a)), result in the formation of tetranuclear diorganotin clusters, {(n-Bu(2)Sn)(2)(OH)(OSO(2)Et)}O (2) and [(Et(2)Sn)(4)(OH)(O)(2)(OSO(2)Me)(3)] (3), respectively. The activation of the Sn-C or S-C bond is not observed in these cases. These findings provide a preliminary insight into the unusual reactivity of 1a under hydrolytic conditions.

摘要

在潮湿的己烷中，混合配体二甲基锡（乙氧基）乙二磺酸盐[Me2Sn(OEt)(OSO2Et)]n（1a）的水解通过歧化和 Sn-C 和 S-C 键的部分断裂进行，生成具有组成[(Me2Sn)(MeSn)4(OSO2Et)2(OH)4(O)2(SO3)2]（1）的新型氧代/羟基金属锡簇，其中含有单和二甲基锡片段以及结构框架中原位生成的亚硫酸根（SO32-）阴离子。另一方面，具有类似混合配体二有机锡前体[R2Sn(OR1)(OSO2R1)]n（R = n-Bu，R1 = Et（2a）；R = Et，R1 = Me（3a））的类似反应导致形成四核二有机锡簇，分别为[{(n-Bu2Sn)2(OH)(OSO2Et)}O]2（2）和[(Et2Sn)4(OH)(O)2(OSO2Me)3]（3）。在这些情况下，没有观察到 Sn-C 或 S-C 键的活化。这些发现为 1a 在水解条件下的异常反应性提供了初步的见解。