title: Matrix isolation spectroscopic and theoretical study of dihydrogen activation by group V metal dioxide molecules.
abstract: The reactions of group V metal dioxide molecules with dihydrogen have been studied by matrix isolation infrared spectroscopy. The ground state VO(2) molecule is able to cleave dihydrogen heterolytically and spontaneously in forming the HVO(OH) molecule in solid argon. In contrast, the reaction of VO(2) with dideuterium to form DVO(OD) proceeds only under UV-visible excitation via a weakly bound VO(2)(η(2)-D(2)) complex. Theoretical calculations predict that the dihydrogen cleavage process is thermodynamically exothermic with a small barrier. The niobium and tantalum dioxide molecules react with dihydrogen to give primarily the side-on bonded metal dioxide bis-dihydrogen complexes, NbO(2)(η(2)-H(2))(2) and TaO(2)(η(2)-H(2))(2), which are further transferred to the HNbO(OH) and HTaO(OH) molecules via photoisomerization in combination with H(2) elimination under UV-visible light excitation.
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China. mfzhou@fudan.edu.cn
authors.forename: Mingfei
authors.initials: M
authors.lastname: Zhou
authors.forename: Caixia
authors.initials: C
authors.lastname: Wang
authors.forename: Jia
authors.initials: J
authors.lastname: Zhuang
authors.forename: Yanying
authors.initials: Y
authors.lastname: Zhao
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng