Insertion reaction of carbon dioxide into Sn–OR bond. Synthesis, structure and DFT calculations of di- and tetranuclear isopropylcarbonato tin(<scp>iv</scp>) complexes
作者:Danielle Ballivet-Tkatchenko、Henry Chermette、Laurent Plasseraud、Olaf Walter
DOI:10.1039/b610812a
日期:——
Sn2O2 ring and the two Sn-OCO2C fragments are nearby coplanar. The same holds for the ladder-type tetranuclear distannoxane. The dimeric structures are also evidenced by solution NMR in non-coordinating solvents. Interestingly, the assignment of the exo and endo tin resonances of the dimeric distannoxane is unambiguous using a labeled 13CO2 experiment. The stability of the dimeric association has been
二氧化碳与锡烷nBu2Sn(OiPr)2和二锡氧烷[nBu2(iPrO)Sn] 2O的反应导致选择性地插入一个Sn-OiPr键,生成相应的nBu2Sn(OiPr)(OCO2(i)Pr)和nBu2 (iPrO)SnOSn(OCO2(i)Pr)nBu2种。两种化合物的特征均在于多核NMR,FT-IR和单晶X射线晶体学。在固态时,它们采用带有桥接的异丙氧基和末端异丙基碳酸酯配体的二聚体排列。双核锡烷的X射线晶体结构表明,Sn2O2环和两个Sn-OCO2C片段位于共面附近。梯型四核二锡氧烷也是如此。还通过在非配位溶剂中的溶液NMR证明了二聚体结构。有趣的是,使用标记的13CO2实验,二聚二氧六六环的外向和内向锡共振的分配是明确的。在DFT计算的基础上,在锡烷系列中探究了二聚体缔合的稳定性。