Singlet hydrocarbon carbenes with high barriers toward isomerization: a computational investigation

Athanassios Nicolaides

doi:10.1021/ja0299699

Singlet hydrocarbon carbenes with high barriers toward isomerization: a computational investigation

J Am Chem Soc. 2003 Jul 30;125(30):9070-3. doi: 10.1021/ja0299699.

Author

Athanassios Nicolaides¹

Affiliation

¹ Contribution from the Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus. athan@ucy.ac.cy

PMID: 15369363
DOI: 10.1021/ja0299699

Abstract

A prerequisite for a stable singlet hydrocarbon carbene is the existence of high barriers toward isomerization. Four derivatives of cyclopentylidene (1-4) with rigid and varying carbon cages are examined computationally at the B3LYP/6-311+G(d,p) level of theory. Singlet ground states are predicted for carbenes 1-4, with DeltaE(ST)'s = 7-22 kcal/mol. The rearrangement paths considered are 1,3-hydrogen shift, 1,2-carbon shift and beta-CC bond-cleavage. Carbenes 3 and 4 lie in relatively shallow potential-energy wells (around 4 and 6 kcal/mol, respectively) and are expected to rearrange via 1,3-hydrogen shifts to cyclopropane derivatives. For 1 and 2, the lowest energy rearrangement path is beta-CC bond-cleavage requiring about 12 and 20 kcal/mol, respectively, placing 2 in the deepest potential-energy well among the four carbenes.