The Lewis Acidity of the BO Triple Bond in Methyl(oxo)­borane1. Issue 7 (11th April 2013)

• Record Type: Journal Article
• Authors: Bettinger, Holger F.; Brough, Sarah; Grunenberg, Jörg
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 639:Issue 7(2013)
• Page Start: 1199
• Page End: 1204
• Publication Date: 2013-04-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201200557
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The interaction of methyl(oxo)borane, CH₃BO, with typical Lewis bases (nitrogen based and N‐heterocyclic carbenes) was investigated using density functional theory (B97‐D, TPSS‐D3), double hybrid density functionals (PWPB95‐D3, B2PLYP‐D3) in conjunction with empirical dispersion corrections, and coupled cluster theory involving singles, doubles, and a perturbative estimate of triple excitations [CCSD(T)]. A polarized quadruple‐zeta basis set was used throughout. The interaction energies computed with the double‐hybrid methods agree very well with CCSD(T). Compared to typical boron Lewis acids, the interaction energies are much smaller for methyl(oxo)borane, indicating that the BO triple bond results in significantly reduced Lewis acidity. An analysis of the mechanical bond strengths in CH₃BO and its complexes indicates that the relaxed BO force constants (compliance constants) and the stretching vibrations decrease with increasing strengths of the dative interactions.</p> </abstract>