Primary and Secondary Processes in the Ultraviolet Photodissociation of CpCo(CO) (Cyclopentadienylcobalt Dicarbonyl).

We investigated the photodissociation dynamics of CpCo(CO) (cyclopentadienylcobalt dicarbonyl) in metal-to-ligand charge transfer (MLCT) bands. By employing DFT calculations, the absorption band (210-240 nm) was characterized as a charge transfer from the Co center to the Cp (cyclopentadienyl, CH) ligand. Ion imaging was utilized to analyze the CO fragments and coordinatively unsaturated complexes (CpCoCO, CpCo, and CoCH) across the entire MLCT band.

Generation of Highly Vibrationally Excited CO in Sequential Photodissociation of Iron Carbonyl Complexes.

Ultraviolet photochemistry of iron pentacarbonyl, Fe(CO), was investigated with resonantly enhanced multiphoton ionization (REMPI) spectroscopy and ion imaging. The REMPI spectrum of CO photofragments, generated by ultraviolet irradiation of Fe(CO), showed the generation in the highly vibrationally excited states with = 11-15. Analysis of the band intensities observed in the 213-235 nm region indicated that the high- CO generation was maximized at around 220 nm.

Primary and Secondary Loss of CO and NO Ligands in the Ultraviolet Photodissociation of the Heteroleptic Co(CO)NO Complex.

The photodissociation dynamics of the heteroleptic Co(CO)NO complex were investigated in the metal-to-carbonyl (CO) ligand charge-transfer band to compare the reactivity of the CO and nitrosyl (NO) ligands. The final state distributions of both the CO and NO fragments were measured using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and velocity-map ion-imaging. The primary CO photofragment was differentiated from the secondary fragments of the subsequent unimolecular decomposition of coordinatively unsaturated intermediates by comparing the momentum distributions.