Primary and Secondary Processes in the Ultraviolet Photodissociation of CpCo(CO)2 (Cyclopentadienylcobalt Dicarbonyl).

Abstract

We investigated the photodissociation dynamics of CpCo(CO)2 (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, C5H5) ligand. Ion imaging was utilized to analyze the CO fragments and coordinatively unsaturated complexes (CpCoCO, CpCo, and CoC3H3) across the entire MLCT band. Measuring the production yields of individual unsaturated complexes as a function of photolysis wavelength by considering wavelength dependence indicated the involvement of several photochemical pathways: the first photodissociation and sequential dissociation of CpCo(CO)2, and the second photodissociation of unsaturated intermediates within the pulse duration of the photolysis laser. The recoil velocity shifts of CpCo and CoC3H3 were attributed to the onset of the sequential dissociation of CpCoCO. Evidence for the second photodissociation of CpCoCO was obtained through the matching of linear momenta between the CO(v = 0, 1) and CpCo fragments. The DFT calculations performed to determine the electronic structures and potential energy curves for photoinduced CO loss in CpCo(CO)2 and CpCoCO supported our interpretation of the experimental results. This study presents a practical approach to selectively detecting specific processes among the mixture of products and intermediates when photolyzing transition-metal carbonyls, as their concurrent generation is unavoidable in laser-based experiments.