title: Experimental and theoretical study of the decomposition of copper nitrate cluster anions.
abstract: Copper nitrate anion clusters Cu(NO3)3(-) and Cu(NO3)2(-) were generated by electrospray ionization and studied with collision-induced dissociation and energy-resolved mass spectrometry. Collision-induced dissociation resulted in three different fragmentation reactions-loss of NO3(-), NO3(•), and NO2(•). The type of fragmentation reaction depends on the oxidation state of the metal. The Cu(NO3)3(-) cluster showed loss of NO3(•) but no loss of NO2(•), whereas the Cu(NO3)2(-) cluster showed loss of NO2(•) but no loss of NO3(•). The fragmentation reactions were studied by theoretical methods. These studies show loss of NO3(•) corresponds to reduction of the metal charge by electron transfer, whereas loss of NO2(•) and metal-oxide bond formation by O(-) abstraction in Cu(NO3)2(-) does not necessarily result in the expected oxidation of the metal.
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487, United States.
authors.forename: Carrie Jo M
authors.initials: CJ
authors.lastname: Pruitt
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Goebbert