title: Electron bridging dihydrogen bond in the imidazole-contained anion derivatives.
abstract: The large contact distance of electron bridging dihydrogen bond (EBDB), which is over 2.4 A, is the most prominent characteristic for the imidazole-contained anion derivatives. The elongation of N-H bond and the shortening of H...H distance can be observed upon hydration and hydrogenation. Transformation from EBDB to dissociative H2 is convenient upon sequential hydrogenation. The H...H distance decreases with the enhancement of the electronegativity of the heavy atom which contacts directly with one of these two hydrogen atoms. NMR shielding of the bonding N varies significantly upon hydration and hydrogenation. The spin-spin coupling constants, 1J(H-H), is dominated predominantly by the paramagnetic spin-orbit and diamagnetic spin-orbit contributions instead of the Fermi-contact term. Enhancement of electronegativity of the heavy atom leads to the increase of 1J(H-H) coupling constants. The stabilization is enhanced upon hydration predominantly for the formation of O-H...N H bond, while it is reversed upon hydrogenation for the cleavage of big pi bond, Pi5(6). Enhancement of the stability is demonstrated by the increase of stabilization energy and vertical electron detachment energy with the electronegativity of the heavy atom. The dominant contributions for the formation of such electron bridging dihydrogen bond are the high polarity of each fragment, large electron density between two fragments, and strong bonding interaction of the bridging electron with H(N) atoms. The H...H interaction can be formed by X-Hdelta+ and Hdelta- -Y polar molecules in Hdelta+...Hdelta- and Hdelta+...e...Hdelta+ of two forms.
authors.affiliation: Institute of Theoretical Chemistry, Shandong University, Jinan 250100, People's Republic of China.
authors.forename: Shihai
authors.initials: S
authors.lastname: Yan
authors.forename: Yuxiang
authors.initials: Y
authors.lastname: Bu
authors.forename: Robert I
authors.initials: RI
authors.lastname: Cukier
mesh_terms: D000838:Anions / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D019281:Dimerization; D004563:Electrochemistry / Q000379:methods; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D007093:Imidazoles / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D011522:Protons; D012984:Software; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D000838:Anions; D007093:Imidazoles; D011522:Protons; C029899:imidazole; D006859:Hydrogen