Thermal and Photolytic Reactions of Group 12 Metal Atoms in HCl-Doped Argon Matrixes: Formation and Characterization of the Hydride Species HMCl (M = Zn, Cd, or Hg)

IR and UV-vis spectroscopic measurements have been used to chart the thermal and photolytic reactions occurring in HCI-doped Ar matrixes containing Zn, Cd, or Hg atoms (M). Following the formation of a loosely bound metalatom adduct M...HCl, the primary reaction induced by UV irradiation (200 ≤ λ ≤ 400 nm) is insertion of M into the H-Cl bond to give the molecule HMCI, which has been characterized by its IR spectrum, with assignments validated by the effects of isotopic change ( 1 , 2 H, 3 5 , 3 7 Cl, and 6 4 , 6 6 , 6 8 Zn) and by the results of density functional theory calculations. The properties of HMCI are compared with those of other Group 12 metal hydrides, and the mechanism of insertion is also discussed.