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The Lewis Acidity of the BO Triple Bond in Methyl(oxo)borane
Author(s) -
Bettinger Holger F.,
Brough Sarah,
Grunenberg Jörg
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200557
Subject(s) - borane , chemistry , lewis acids and bases , coupled cluster , frustrated lewis pair , density functional theory , basis set , triple bond , computational chemistry , london dispersion force , boron , cluster (spacecraft) , boranes , double bond , crystallography , molecule , organic chemistry , van der waals force , computer science , programming language , catalysis
The interaction of methyl(oxo)borane, CH 3 BO, 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 CH 3 BO and its complexes indicates that the relaxed BO force constants (compliance constants) and the stretching vibrations decrease with increasing strengths of the dative interactions.