title: Dihydrogen bonding vs metal-σ interaction in complexes between H2 and metal hydride.
abstract: The complexes formed by hydrogen with metal hydrides (LiH, NaH, BeH(2), MgH(2), BH(3), AlH(3), Li(2)H(2), Na(2)H(2), Be(2)H(4), and Mg(2)H(4)) have been theoretically studied at the MP2/aug-cc-pVTZ, MP2/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ levels of theory. The hydrogen molecule can act as a Lewis acid or base. In the first case, a dihydrogen bonded complex is obtained and in the second an interaction between the σ-bond of the hydrogen molecule and an empty orbital of the metal atoms is found. Quantum theory of atoms in molecules and natural bond orbitals methods have been applied to analyze the intermolecular interactions. Additionally, the cooperativity effects are analyzed for selected complexes with two H(2) molecules where both kinds of interactions exist simultaneously.
authors.affiliation: Instituto de Química Médica (CSIC), Juan de la Cierva, 3, 28006 Madrid, Spain. ibon@iqm.csic.es
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.forename: Jose
authors.initials: J
authors.lastname: Elguero
authors.forename: Mohammad
authors.initials: M
authors.lastname: Solimannejad
authors.forename: Sławomir J
authors.initials: SJ
authors.lastname: Grabowski
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D058116:Lewis Acids / Q000737:chemistry; D058115:Lewis Bases / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory
chemical_list: D058116:Lewis Acids; D058115:Lewis Bases; D008670:Metals; D006859:Hydrogen