title: Characteristics and nature of the intermolecular interactions in boron-bonded complexes with carbene as electron donor: an ab initio, SAPT and QTAIM study.
abstract: We report geometries, stabilization energies, symmetry adapted perturbation theory (SAPT) and quantum theory of atoms in molecules (QTAIM) analyses of a series of carbene-BX(3) complexes, where X = H, OH, NH(2), CH(3), CN, NC, F, Cl, and Br. The stabilization energies were calculated at HF, B3LYP, MP2, MP4 and CCSD(T)/aug-cc-pVDZ levels of theory using optimized geometries of all the complexes obtained from B3LYP/aug-cc-pVTZ. Quantitatively, all the complexes indicate the presence of B-C(carbene) interaction due to the short B-C(carbene) distances. Inspection of stabilization energies reveals that the interaction energies increase in the order NH(2) > OH > CH(3) > F > H > Cl > Br > NC > CN, which is the opposite trend shown in the binding distances. Considering the SAPT results, it is found that electrostatic effects account for about 50% of the overall attraction of the studied complexes. By comparison, the induction components of these interactions represent about 40% of the total attractive forces. Despite falling in a region of charge depletion with nabla(2)ρ(BCP) >0, the B-C(carbene) bond critical points (BCPs) are characterized by a reasonably large value of the electron density (ρ(BCP)) and H(BCP) <0, indicating that the potential energy overcomes the kinetic energy density at BCP and the B-C(carbene) bond is a polar covalent bond.
authors.affiliation: Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran. esrafili@maragheh.ac.ir
authors.forename: Mehdi D
authors.initials: MD
authors.lastname: Esrafili
mesh_terms: D001895:Boron / Q000737:chemistry*; D001896:Boron Compounds / Q000737:chemistry*; D004583:Electrons; D006860:Hydrogen Bonding; D007700:Kinetics; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D001896:Boron Compounds; C030011:carbene; D001895:Boron; D008697:Methane