Journal of Physical Chemistry A, Vol.110, No.47, 12785-12792, 2006
Group 4 transition-metal atom reactions with CS2 and OCS: Infrared spectra and density functional calculations of SMCS, SM-(eta(2)-CS), SMCO, and OMCS in solid argon
Laser-ablated titanium, zirconium, and hafnium atoms were reacted with CS2 and OCS molecules during condensation in excess argon. With CS2, the SMCS and S-M(eta(2)-CS) products were formed on sample deposition. Photolysis increased both complexes, while annealing favored the lower energy S-M(eta(2)-CS) side-bound isomer. The OCS reactions produced SMCO, OMCS, and the simple M(eta(2)-CO)S adduct. Product absorptions are identified by comparison with density functional theory frequency calculations and isotopic substitutions. Investigations with OCS emphasized differences in the CS and CO bond insertion products.