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

Journal of the American Chemical Society
Athanassios Nicolaides

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.

References

May 18, 2000·The Journal of Organic Chemistry·L L StracenerW L Karney
Dec 26, 2001·Chemical Reviews·Didier BourissouGuy Bertrand
Jan 17, 2002·Journal of the American Chemical Society·Hideo TomiokaKatsuyuki Hirai
Aug 31, 2002·Angewandte Chemie·Emmanuelle DespagnetGuy Bertrand

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Citations

Oct 1, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Natalie FeyA Guy Orpen
Dec 7, 2006·Journal of the American Chemical Society·Jean-Luc Mieusset, Udo H Brinker

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