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).

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 …”

Reduction of Acetonitrile by Hydrated Magnesium Cations Mg+(H2O)n (n≈20–60) in the Gas Phase

“…[17] Coordination chemistry and charge transfer of hydrated transition-metal ions have been investigated in reactions with O 2 , CO 2 , and N 2 O [18] as well as with NO. [19] Mg + (H 2 O) n are certainly among the best-studied singly charged hydrated metal ions in the gas phase.…”

Infrared Multiple Photon Dissociation Spectroscopy of Hydrated Cobalt Anions Doped with Carbon Dioxide CoCO2(H2O)n−, n=1–10, in the C−O Stretch Region

“…[14] Some hydrated metal ions M + (H 2 O) n ,M= Mg, Cr,C o, pick up exactly one CO 2 molecule, indicating that electron transfer from the metal to carbon dioxide takes place. [66][67][68] In the case of magnesium, the electron is already present in the hydration shell, detached from the metal center, as recently confirmed by electronic spectroscopy of Mg + (H 2 O) n . [69] For the structural analysis of hydrated metal ions M(H 2 O) n (M = Li + ,N a + ,M g + ,M g 2 + ,A l + ,C a 2 + ,C o + ,C o 2 + ,C u + ,A g + , Cs + ,B a 2 + ,T m 3 + ,L a 3 + ), as eries of infrared photodissociation studies are available.…”