Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

Abstract

Electrospray ionization (ESI) of aqueous cobalt(II) and nickel-(II) nitrate solutions inter alia affords the solvated, mono-and oligonuclear nitrato complexes [M m + (M = Co, Ni; m = 1-5; n = 1-4). The collision-induced dissociation spectra of the mass-selected ions imply that these ions correspond to genuine hydrated metal(II) nitrato complexes in that either cluster degradation through expulsion of neutral M(NO 3 ) 2 or sequential loss of water ligands take place. In the case of the lowest member of the series (m, n = 1), however, loss of water competes with homolytic cleavage of the N-O bond, which leads to the formation of [M,O 2 ,H 2 ] + cat-

Experimental and Theoretical Study of the Decomposition of Copper Nitrate Cluster Anions

“…The type of fragmentation reaction depends on the oxidation state of the metal. The Cu(NO 3 ) 3 − cluster showed loss of NO 3 • but no loss of NO 2 • , whereas the Cu(NO 3 ) 2 − cluster showed loss of NO 2…”

“…2 These experiments were recently reinvestigated by Franśki et al using quadrupole time-of-flight (TOF) mass spectrometer for collision-induced dissociation (CID). 1 Both studies reported the loss of NO 3 − , NO 3 • , and NO 2 • as the primary decomposition pathways for many transition metal nitrate cluster anions. Specific reactions varied depending on the charge of the metal.…”

“…The fragmentation reactions were studied by theoretical methods. These studies show loss of NO 3 • corresponds to reduction of the metal charge by electron transfer, whereas loss of NO 2 • and metal−oxide bond formation by O − abstraction in Cu(NO 3 ) 2 − does not necessarily result in the expected oxidation of the metal.…”

“…, NO 3 • , and NO 2 • . The type of fragmentation reaction depends on the oxidation state of the metal.…”

Synthesis and Structures of Plutonyl Nitrate Complexes: Is Plutonium Heptavalent in PuO3(NO3)2– ?

“…The decomposition of gas-phase metal nitrate anions, M(NO 3 ) n − , can result in the elimination of neutral NO 2 , producing MO(NO 3 ) n−1 − . [12][13][14] In cases where higher oxidation states of the metal are accessible than that in the nitrate precursor, oxidation of the metal center can occur during these processes. would similarly comprise Pu(VII).…”