Reactions of Co, Ni, and Cu Atoms with CS2: Infrared Spectra and Density-Functional Calculations of SMCS, M-(η2-CS)S, M-CS2, and MCS2+ in Solid Argon

Laser-ablated cobalt, nickel, and copper atoms and cations were reacted with CS 2 molecules during condensation in excess argon. The carbon-bonded M−η 1 -CS 2 and side-bonded M−(η 2 -CS)S complexes were formed on annealing, whereas the inserted SMCS molecules were formed on photolysis. The Co−η 1 -CS 2 +, Ni−η 1 -CS 2 + and Cu−SCS + cations were also produced by metal cation reactions with CS 2 . The product absorptions are identified by isotopic substitutions, electron trapping with added CCl 4, and density functional calculations. This work provides the first vibrational spectroscopic characterization of the Co, Ni, and Cu−CS 2 neutral and cation complexes and the SMCS insertion products.