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The Key Role of Orbital Interaction in Cooperativity between B⋅⋅⋅N and Hydrogen/Lithium Bonding: An ab initio Study
Author(s) -
Esrafili Mehdi D.,
Mousavian Parisasadat
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701309
Subject(s) - cooperativity , chemistry , hydrogen bond , ternary operation , lithium (medication) , crystallography , ab initio , molecule , cooperative binding , natural bond orbital , binding energy , molecular orbital , computational chemistry , binding site , atomic physics , organic chemistry , physics , medicine , biochemistry , computer science , programming language , endocrinology
The aim of this study is to investigate the possible cooperative effects between B⋅⋅⋅N and hydrogen‐ or lithium‐bonding interactions in the ternary H 3 B⋅⋅⋅NCM⋅⋅⋅Z, F 3 B⋅⋅⋅NCM⋅⋅⋅Z and C 5 H 5 B⋅⋅⋅NCM⋅⋅⋅Z complexes, where M=H, Li and Z= NH 3 , N 2 . The characteristic of the interactions in these complexes is studied by molecular electrostatic potential, quantum theory of atoms in molecules and natural bond orbital analyses. For all these complexes, the M⋅⋅⋅N binding distances are always shorter than those in NCM⋅⋅⋅Z binary complexes, which implies that the formation of the B⋅⋅⋅N interaction strengthens the M⋅⋅⋅N bonds. However, unlike H 3 B⋅⋅⋅NCM⋅⋅⋅Z and F 3 B⋅⋅⋅NCM⋅⋅⋅Z complexes, the B⋅⋅⋅N binding distances in C 5 H 5 B⋅⋅⋅NCM⋅⋅⋅Z are found to be longer than those in C 5 H 5 B⋅⋅⋅NCM dimers. Such unusual cooperativity between the B⋅⋅⋅N and hydrogen‐ or lithium‐bonding interactions has not been reported previously. The origin of this unusual cooperativity between B⋅⋅⋅N and M⋅⋅⋅N interactions in C 5 H 5 B⋅⋅⋅NCM⋅⋅⋅Z complexes is explained in term of the back‐bonding π→ π * charge‐transfer between C 5 H 5 B and NCM moieties.