A Class of Computationally Designed Tri-Coordinate Cyclic Silylenes RSi(mu-R)(2)AIR(2)

作者：Xu Jing; Ding Yi Hong^*

来源：Australian Journal of Chemistry, 2014, 67(5): 740-748.

DOI：10.1071/CH13489

With the aim of designing novel low-valent silylenes, herein we report the first systematic investigation of the SiAlR5 system. Based on the 'topology' isomeric search strategy, four classes of isomers, i.e. RSi(mu-R)(2)AlR2 1, R3Si-AlR2 2, R2Si(mu-R)AlR2 3, and R2Si-AlR3 4 were identified. For 12 groups with an electron lone-pair, i.e. R = F, NH2,OH, SH, OMe, PMe2, SMe, OEt, PEt2, SEt, OPh, and PPh2, the tri-coordinate silylene 1 is the most stable structure, which contains two sets of intermolecular donor-acceptor interactions. In accordance with the 'silylene' term, the Si-centre can undergo both a nucleophilic reaction and insertion reaction. Moreover, coupling AlR3 (R = OR ' and PR '(2)) (R ' = H, Me, Et, and Ph) with the known cyclic di-coordinate silylene could lead to stable tri-coordinate silylenes. These novel tri-coordinate silylenes strongly welcome laboratory studies in near future.

• 出版日期2014
• 单位吉林大学