title: Reactivity of hydrated monovalent first row transition metal ions M(+)(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward molecular oxygen, nitrous oxide, and carbon dioxide.
abstract: The reactions of hydrated monovalent transition metal ions M(+)(H(2)O)(n), M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward molecular oxygen, nitrous oxide, and carbon dioxide were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Clusters containing monovalent chromium, cobalt, nickel, or zinc were reactive toward O(2), while only hydrated cobalt was reactive toward N(2)O. A strongly size dependent reactivity was observed. Chromium and cobalt react very slowly with carbon dioxide. Nanocalorimetric analysis, (18)O(2) exchange, and collision induced dissociation (CID) experiments were done to learn more about the structure of the O(2) products. The thermochemistry for cobalt, nickel, and zinc is comparable to the formation of O(2)(-) from hydrated electrons. These results suggest that cobalt, nickel, and zinc are forming M(2+)/O(2)(-) ion pairs in the cluster, while chromium rather forms a covalently bound dioxygen complex in large clusters, followed by an exothermic dioxide formation in clusters with n ≤ 5. The results show that hydrated singly charged transition metal ions exhibit highly specific reactivities toward O(2), N(2)O, and CO(2).
authors.affiliation: Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstraße 40, 24098 Kiel, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: van der Linde
authors.forename: Sonja
authors.initials: S
authors.lastname: Hemmann
authors.forename: Robert F
authors.initials: RF
authors.lastname: Höckendorf
authors.forename: O Petru
authors.initials: OP
authors.lastname: Balaj
authors.forename: Martin K
authors.initials: MK
authors.lastname: Beyer
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D013058:Mass Spectrometry; D009609:Nitrous Oxide / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D028561:Transition Elements; D014867:Water; D002245:Carbon Dioxide; D009609:Nitrous Oxide; D010100:Oxygen