✦ LIBER ✦

Internal conrotation and disrotation in H2BCH2BH2 and diborylmethane 1,3 H exchange

✍ Scribed by Minyaev, Ruslan M.; Quapp, Wolfgang; Subramanian, Govindan; Schleyer, Paul von R.; Mo, Yirong

Book ID: 101220673
Publisher: John Wiley and Sons
Year: 1997
Tongue: English
Weight: 416 KB
Volume: 18
Category: Article
ISSN: 0192-8651
DOI: 10.1002/(sici)1096-987x(19971115)18:14<1792::aid-jcc8>3.0.co;2-f

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✦ Synopsis

The paths of correlated internal disrotation barrier less than 0.4 . Ž . kcalrmol and conrotation barrier around 1.9 kcalrmol of the two BH groups 2 w Ž . x in H BCH BH have been computed employing ab initio MP2 full r6᎐31G** 2 2 2 Ž . and density functional theory Becke3LYPr6᎐311qG** methods. Two Ž . B-C иии B p hyperconjugative interactions stabilize the C symmetric s Ž . Ž . H BCH BH isomer 1 . The B-C иии B p hyperconjugative stabilization, 2 2 2 evaluated by homodesmotic reactions and using the orbital deletion procedure Ž . which ''deactivates'' the '' vacant'' born p orbital , is less than 6 kcalrmol in Ž . diborylmethane. The B-C иии B p stabilization is shown to be remarkably large Ž . Ž . in C B H Td . At MP2 fu r6᎐31G**, disproportionation into 1 and methane 4 6 10 is only 5.6 kcalrmol exothermic. The 1,3 H exchange in diborylmethane is an asynchronous process and proceeds via a doubly bridged cyclic intermediate with 9.3 kcalrmol barrier. Structures with ''planar tetracoordinate'' carbon are stabilized considerably by BH substituents, but they are still high in energy.

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