Reactions of M⁺(H₂O)_n, n < 40, M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, with D₂O Reveal Water Activation in Mn⁺(H₂O)_n

Abstract

Reactions of M(+)(H(2)O)(n), n < 40, M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, with D(2)O are studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Isotopically highly enriched metals are used as applicable. Isotopic scrambling with formation of HDO is not observed for M = Cr, Fe, Co, Ni, Cu, and Zn, which indicates that these hydrated metal ions consist of a singly charged metal center and a hydration shell of intact, inactivated water molecules. In the vanadium case, HDO formation is observed in the size region where also hydroxide formation with evolution of molecular hydrogen occurs. For manganese, HDO formation occurs in the size regime n ≈ 8-20. Additional experiments show that, in this size regime, Mn(+)(H(2)O)(n) is slowly converted into HMnOH(+)(H(2)O)(n-1) under the influence of room temperature blackbody radiation. The reaction is mildly exothermic; ΔH ≈ -21 ± 10 kJ mol(-1).

Recent Advances in the Synthesis, Characterization and Application of Zn+‐containing Heterogeneous Catalysts

“…Such gas phase Zn + species were of little use for practical applications. A new class of Zn + complexes, including Zn + (H 2 O) n and Zn + (H 2 ) n , were also obtained in an external laser vaporization source, though the physical properties and chemical reactions of these complexes remained unexplored for a long time …”

Microsolvation of Zn cations: infrared multiple photon dissociation spectroscopy of Zn+(H2O)n (n = 2–35)

“…81 No H/D exchange was found in reactions with D 2 O. 45 An intriguing chemistry was found with NO, where HNO and ZnOH + (H 2 O) m is formed following the initial uptake of one NO molecule, i.e. the reaction or the evaporation of HNO is delayed and occurs preferentially for n E 15-20 water molecules.…”

Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

“…26 In addition, van der Linde and Beyer have examined water activation in larger clusters of M + (H 2 O) n (n < 40) (M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn) in a FT-ICR mass spectrometer, with particular emphasis on water activation in Mn + (H 2 O) n . 27 O Brien and Williams used vibrational spectroscopy to observe similar effects in smaller divalent clusters (n = 5-8). 28 Rosi and Bauschlicher have investigated binding energies of M + (H 2 O) n (n = 1-4) for transition metals from V to Zn.…”