Reactivity of Carbon Dioxide with <i>n</i>-Butyl(phenoxy)-, (alkoxy)-, and (oxo)stannanes: Insight into Dimethyl Carbonate Synthesis
作者:Danielle Ballivet-Tkatchenko、Olivier Douteau、Stefanie Stutzmann
DOI:10.1021/om000397f
日期:2000.10.1
Bu2Sn(OMe)(OCO2iPr), selectively. Facile deinsertion of CO2 is a common property of all compounds, occurring more readily in the dibutyl series. The stoichiometric transformation of the carbonato ligand in 2b, 5b, or 6b to dimethyl carbonate (DMC) on reaction with MeI requires nucleophilic assistance by F- to proceed. In the presence of MeOH, 2b and 5bare almost inactive forDMC formation, in contrast with 6b. The best
该CO 2插入一系列丁基(苯氧基)的Sn-O的键- ,(烷氧基) - ,和(氧代)锡烷进行了研究。三丁基衍生物Bu 3 SnOR(2a,R = Me; 3a,R = i Pr; 4a,R = t Bu; 5a,R = SnBu 3)1定量给出Bu 3 Sn(OCO 2 R),2b - 5b ; 类似的三丁基苯氧基锡烷1的反应性较低。对于二丁基系列Bu 2 Sn(OR)2,t的空间效应OR(8a)中的Bu基团在大气压下抑制碳化。与R =我(图6a)或R =我PR(图7a)中,只有一个的Sn-OR键的反应,导致卜2的Sn(OR)(OCO 2 R),图6b或7b中。用2-丙醇处理6a在CO 2下选择性地提供混合的化合物Bu 2 Sn(OMe)(OCO 2 i Pr)。简便的CO 2脱嵌是所有化合物的共同特性,在二丁基系列中更容易发生。碳酸盐配体在2b,5b中的化学计量转化或图6b对用MeI反应的