Contrasting products in the reactions of Cr, Mo, and W atoms with H2O2:: Argon matrix infrared spectra and theoretical calculations

Products in the reactions of H2O2 and H-2, O-2 mixtures have been observed by matrix infrared absorptions and identified through comparisons with vibrational frequencies calculated for these molecules. The chromium reactions are dominated by lower oxidation state products, whereas molybdenum and tungsten chemistry favors higher oxidation state products. For example chromium dihydroxide, Cr(OH)(2), molybdenum hydride oxide, H2MoO2, and tungsten hydride oxide, H2WO2, were observed in laser-ablated metal atom reactions with H2O2, and calculations show that these are the most stable molecules for this stoichiometry. Chromium monohydroxide, CrOH, was identified through O-H and Cr-O stretching modes, while HWO was observed by W-H and W=O stretching modes. The metal oxyhydroxides, HMO(OH), were observed for all metals. However, reactions with two H2O2 molecules give OCr(OH)(2), MoO2(OH)(2), and WO2(OH)(2). The relative stabilities of different structures for Cr, Mo, and W are due to different participations of occupied d orbitals. The reactivity of the cold metal atoms with H2O2 on annealing the solid argon matrix increases on going down the group.