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Computational Study of the Isomerization Reactions of Borirane

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journal contribution
posted on 2018-01-31, 19:52 authored by Małgorzata Krasowska, Holger F. Bettinger
Borirane is isoelectronic to the cyclopropyl cation, but is stable toward electrocyclic ring opening to 2-bora-propa-1,3-diyl A, the boron analogue of the allyl cation. A computational investigation using density functional theory (B3LYP) in combination with highly correlated electronic structure theory methods of the coupled-cluster [CCSD­(T)] and multireference configuration interaction (MRCI) type in conjunction with basis sets of up to quadruple-ζ quality reveal that formation of A is endothermic by roughly 15 kcal mol–1 and that A collapses almost without barrier (0.2 kcal mol–1) to borirane. The vinylborane isomer B is more stable than borirane and its formation is associated with a barrier of 36–38 kcal mol–1. Methyl methylideneborane E, only slightly less stable than B, can only be accessed by pathways involving barriers of at least 60 kcal mol–1.