The cubyl cation rearrangements.

作者信息

Jalife Said, Mondal Sukanta, Cabellos Jose Luis, Martinez-Guajardo Gerardo, Fernandez-Herrera Maria A, Merino Gabriel

机构信息

Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida. Km 6 Antigua Carretera a Progreso. Apdo. Postal 73, Cordemex, 97310, Mérida, Yuc., Mexico.

出版信息

Chem Commun (Camb). 2016 Feb 25;52(16):3403-5. doi: 10.1039/c5cc10568d.

DOI:10.1039/c5cc10568d

PMID:26880646

Abstract

Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures.

摘要