Experimental and Theoretical Studies on Structures and Reactivity of the Kinetically Stabilized Silaaromatics

Abstract

Recently, we have reported the synthesis of the first stable silabenzene, 1-silanaphthalene, 2-silanaphthalene, and 9-silaanthracene utilizing kinetic stabilization afforded by an efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt). Here, the experimental and theoretical studies on structures and reactions of silaaromatics will be described. Although it was found that the silaaromatics have considerable aromaticity by taking account of their structural feature into consideration, these silaaromatics readily undergo 1,2- and/or 1,4-addition reactions with MeOH, acetylene derivatives, nitrile oxides, CCl₄ and so on. Detailed studies on the selectivity of these addition reactions based on the results of experiments and theoretical calculations will be presented. In addition, dimerization reactions and photochemical isomerization reactions of silaaromatics will be described.