Triplet H-C-SiHCl(2): combined matrix-IR and CCSD(T) identification, and the role of the open-shell singlet state.
Triplet carbene H-C-SiHCl(2) (1), prepared by a photochemical [1,2]H-shift from 1,1-dichlorosilaethylene, was identified by matching experimental and [CCSD(T)/cc-pVTZ] infrared absorptions. Parts of the potential energy surface were explored utilizing CCSD(T)/cc-pVTZ and B3LYP/6-311+G computations. DFT reproduces the experimental features and CCSD(T) computations for the triplet surface but fails in the description of the open-shell singlet state of 1. We emphasize the notion of electropositive heterosubstitution for the generation of persistent ground-state triplet carbenes.
Schreiner
Peter R
PR
Institute of Organic Chemistry, Justus-Liebig-University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany. prs@org.chemie.uni-giessen.de
Reisenauer
Hans Peter
HP
Allen
Wesley D
WD
Sattelmeyer
Kurt W
KW