A Stable Silicon Congener of Highly Strained Bicyclo[3.2.0]hepta-1,3,6-triene

Publisher Website
Google Scholar
Abstract
A silicon-containing fused bicyclic compound with a highly strained bridgehead double bond, 2,3,6,7-tetra-tert-butyl-4-(tert-butyldimethylsilyl)-5-(tert-butyldimethylsiloxy)-5-silabicyclo[3.2.0]hepta-1,3,6-triene (2), was synthesized quantitatively by the reaction of 1,2-bis-tert-butyl-4,4-bis(tert-butyldimethylsilyl)-4-silatriafulvene (3) with di-tert-butylcyclopropenone (4) at 80 degrees C. An X-ray crystallographic analysis for 2 not only confirmed a bicyclic structure having a silacyclopentadiene (silole) ring fused with a silacyclobutene ring but also the remarkable deformation around the double bonds; the sum of the bond angles around the unsaturated bridgehead carbon was 333 degrees . The strain energy of a model 5-silabicyclo[3.2.0]hepta-1,3,6-triene was calculated at the MP2/6-31+G(d,p)//B3LYP/6-31+G(d) level (30.2 kcal/mol) to be comparable to that for parent bicyclo[3.2.0]hepta-1,3,6-triene (30.7 kcal/mol). Despite the high steric strain, 2 was stable enough to be kept intact for several months in the air. The high stability is ascribed to the effective steric protection of the ring system by the bulky substituents.