title: Mechanism of heterolysis of H2 by an unsaturated d8 nickel center: via tetravalent nickel?
abstract: Collision of H(2) with the unusual nickel complex, (PNP)Ni(+), where PNP = ((t)Bu(2)PCH(2)SiMe(2))(2)N, forms a rare dihydrogen complex of the d(8) configuration which then rearranges to heterolytically cleave the H-H bond. Experimental studies support a short H/H distance in the coordinated diatomic, and DFT calculations show that the transition state for heterolysis, in spite of the fact that this involves an amide nitrogen located trans to the H(2), has the H/H bond fully split, and has all the geometric features of Ni(IV), but this is a local maximum, not a minimum.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Tao
authors.initials: T
authors.lastname: He
authors.forename: Nikolay P
authors.initials: NP
authors.lastname: Tsvetkov
authors.forename: José G
authors.initials: JG
authors.lastname: Andino
authors.forename: Xinfeng
authors.initials: X
authors.lastname: Gao
authors.forename: Benjamin C
authors.initials: BC
authors.lastname: Fullmer
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton