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Download fileComputational Study of the Isomerization Reactions of Borirane
journal contribution
posted on 2018-01-31, 19:52 authored by Małgorzata Krasowska, Holger F. BettingerBorirane 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.
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Keywords
Computational Studybasis sets-ζ qualityMethyl methylideneborane Ebarriermolelectrocyclic ring openingcyclopropyl cationB 3LYPallyl cationstructure theory methodsIsomerization ReactionsformationboriraneMRCImultireference configuration interactionBorirane Boriraneboron analogueCCSDvinylborane isomer Bkcal