title: Complexes between dihydrogen and amine, phosphine, and arsine derivatives. Hydrogen bond versus pnictogen interaction.
abstract: A theoretical study of the complexes between dihydrogen, H2, and a series of amine, phosphine, and arsine derivatives (ZH3 and ZH2X, with Z = N, P, or As and X = F, Cl, CN, or CH3) has been carried out using ab initio methods (MP2/aug-cc-pVTZ). Three energetic minima configurations have been characterized for each case with the H2 molecule in the proximity of the pnictogen atom (Z). In configuration A, the σ-electrons of H2 interact with σ-hole region of the pnictogen atom generated by the of X-Z bond. These complexes can be ascribed as pnictogen bonded. In configuration C, the lone electron pair of Z acts as the Lewis base, and H2 plays the role of the Lewis acid. Finally, configuration B presents a variety of noncovalent interactions depending on the binary complex considered. The atoms-in-molecules theory (AIM), natural bond orbitals (NBO) method as well as the density functional theory-symmetry adapted perturbation theory (DFT-SAPT) approach were used in this study to deepen the nature of the interactions considered.
authors.affiliation: Faculty of Chemistry, University of the Basque Country UPV/EHU, and Donostia International Physics Center (DIPC), P.K. 1072, 20080, Donostia, Spain. s.grabowski@ikerbasque.org
authors.forename: Sławomir J
authors.initials: SJ
authors.lastname: Grabowski
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.forename: José
authors.initials: J
authors.lastname: Elguero
mesh_terms: D000588:Amines / Q000737:chemistry*; D001152:Arsenicals / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D010720:Phosphines / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000588:Amines; D001152:Arsenicals; D010720:Phosphines; D006859:Hydrogen; C006633:arsine