Infrared Spectra of CH3−NbF, CH2NbHF, and CH⋮NbH2F- Formed by Reaction of Methyl Fluoride with Laser-Ablated Niobium Atoms

Abstract

Simple methyl, methylidene, and anionic methylidyne niobium complexes (CH3−NbF, CH2NbHF, and CH⋮NbH2F-) are produced in reactions of laser-ablated niobium atoms and methyl fluoride and isolated in an argon matrix. All three products are formed by co-deposition of the metal atoms and methyl fluoride, but the methylidene complex is heavily favored. The methylidene concentration increases further following visible and UV irradiations, whereas the methyl and methylidyne complexes are depleted on visible and UV irradiations, respectively. This work reports the first experimental evidence for a group V anionic methylidyne complex (CH⋮NbH2F-), which is eliminated by the addition of CCl4 to capture electrons formed in the ablation process. The DFT calculations show that one of the α-hydrogen atoms in CH2NbHF is considerably bent toward the metal atom, an evidence of strong agostic interaction in the doublet ground state and provide isotopic frequencies for matching with observed values.