Persistent photo-reversible transition-metal methylidene system generated from reaction of methyl fluoride with laser-ablated zirconium atoms and isolated in a solid argon matrix

A photoreversible transition-metal methylidene system has been formed for the first time by reaction of methyl fluoride and laser-ablated Zr atoms, isolated in solid argon, and investigated by means of infrared spectroscopy. Four different groups of absorptions are characterized on the basis of behaviors upon broad-band irradiation and sample annealing. Growth of Group I is accompanied by demise of Group II on irradiation with visible light (lambda > 530 nm) and vice versa with UV light (240 < lambda < 380 nm). The methylidene complex CH2=ZrHF is responsible for Groups I and II either in different singlet-triplet spin states or argon matrix packing configurations. The ground singlet state is stabilized by an agostic interaction. On the other hand, Group 111, which arises from the Grignard type compound CH3-ZrF, disappears upon irradiation of UV light (lambda > 380 nm), increasing the concentration of CH2=ZrHF by alpha-H elimination. Fragments of methyl fluoride such as the CH2F radical comprise Group IV. Theoretical calculations are carried out for the alkylidene complex and other plausible products, and the results are compared with the experimental frequencies.