INFRARED PHOTODISSOCIATION SPECTROSCOPY OF FIRST ROW TRANSITION METAL-CARBONYL CATIONS

Author Institution: Department of Chemistry, University of Georgia, Athens, GA 30602-2256Transition metal-carbonyl cations are generated in a laser vaporization/supersonic expansion cluster source, mass selected and studied using infrared laser photodissociation spectroscopy. The carbonyl stretching region (2050-2350 cm$^{-1}$) is probed using a tunable infrared OPO/OPA system. Several cluster sizes are investigated and insight into their stability and geometry is obtained. Cu(CO)$_4^{+}$ has a complete coordination sphere, consistent with 18-electron stability and a tetrahedral structure similar to that of isovalent Ni(CO)$_4$. Ti(CO)$_6^{+}$ has a complete coordination sphere and does not satisfy the 18-electron rule. DFT calculations are performed and reported to corroborate the experimental data