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σ‐Hole Opposite to a Lone Pair: Unconventional Pnicogen Bonding Interactions between ZF 3 (Z=N, P, As, and Sb) Compounds and Several Donors
Author(s) -
Bauzá Antonio,
Mooibroek Tiddo J.,
Frontera Antonio
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600073
Subject(s) - lone pair , natural bond orbital , chemistry , counterintuitive , crystallography , computational chemistry , density functional theory , physics , molecule , quantum mechanics , organic chemistry
Abstract The ability of several pnicogen sp 3 derivatives ZF 3 (Z=N, P, As, Sb) to interact with electron‐rich entities by means of the opposite face to the lone pair (lp) is investigated at the RI‐MP2/aug‐cc‐pVQZ level of theory. The strength of the interaction ranges from −1 to −87 kJ mol −1 , proving its favorable nature, especially when the lp is coordinated to a metal center, whereby the strength of the interaction is significantly enhanced. NBO analysis showed that orbital effects are modest contributors to the global stabilization of the pnicogen σ‐hole bonded complexes studied. Finally, a selection of Cambridge Structural Database examples are shown that demonstrate the impact of this counterintuitive binding mode in the solid state.