Reactions of Laser-Ablated Fe, Co, and Ni with NO: Infrared Spectra and Density Functional Calculations of MNO+ and M(NO)x (M = Fe, Co, x = 1−3; M = Ni, x = 1, 2), and M(NO)x- (M = Co, Ni; x = 1, 2)

Abstract

Laser-ablated iron, cobalt, and nickel atoms, cations, and electrons have been reacted with NO molecules during condensation in excess neon and argon. The end-on bonded Fe(NO)1-3, Co(NO)1-3, and Ni(NO)1-2 nitrosyls and side-bonded Fe−(η2-NO), Co−(η2-NO), and Ni−(η2-NO) species are formed during sample deposition or on annealing. The FeNO+, CoNO+, and NiNO+ mononitrosyl cations are also produced via metal cation reactions with NO. Evidence is also presented for the Ni(NO)1,2- and Co(NO)1,2- anions. The product absorptions are identified by isotopic substitution (15N16O, 15N18O, and mixtures), electron trapping with added CCl4, and density functional calculations of isotopic frequencies. This work provides the first vibrational spectroscopic characterization of Fe, Co, and Ni nitrosyl cations and anions.