A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene
Shaozhi Du, Fanshu Cao, Xi Chen, Rong Hua, Haibin Song, Zhenbo Mo
Abstract
Abstract Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Herein, we report the synthesis of a silylene-stabilized ditin(0) complex ( 2 ) by reduction of a silylene-supported dibromostannylene ( 1 ) with 1 equivalent of magnesium (I) dimer in toluene. The structure of 2 was established by single crystal X-ray diffraction analysis. Density Functional Theory calculations revealed that complex 2 bears a Sn=Sn double bond and one lone pair of electrons on each of the Sn(0) atoms. Remarkably, complex 2 is readily methylated to give a mixed-valent methylditin cation ( 4 ), which undergoes topomerization in solution though a reversible 1,2-Me migration along a Sn=Sn bond. Computational studies showed that the three-coordinate Sn atom in 4 is the dominant electrophilic center, and allows for facile reaction with KHBBu s 3 furnishing an unprecedented N-heterocyclic silylenes-stabilized distannavinylidene ( 5 ). The synthesis of 2 , 4 and 5 demonstrates the exceptional ability of N-heterocyclic silylenes to stabilize low valent tin complexes.