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

Ultraviolet photochemistry of iron pentacarbonyl, Fe(CO)₅, 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)₅, showed the generation in the highly vibrationally excited states with v = 11-15. Analysis of the band intensities observed in the 213-235 nm region indicated that the high-v CO generation was maximized at around 220 nm. Generation yields of the coordinatively unsaturated intermediates, Fe(CO), were measured as a function of the photolysis wavelength using a nonresonant detection scheme. The yield spectrum of FeCO was correlated with that of the high-v CO fragments, suggesting high-v CO generation in the photodissociation of FeCO. The density functional theory calculations of the excited states of FeCO showed an intense photoabsorption to the metal-centered state near 220 nm. The theoretical results were consistent with the interpretation of FeCO + hν → Fe + high-v CO, which was experimentally indicated. The momentum distribution obtained from the velocity distributions of Fe, Fe(CO)₄, and CO fragments further supported that Fe is the counter-product of the high-v CO fragment. The present results provided selective observation of the photochemistry of the unsaturated iron carbonyl complexes, which has not been well elucidated in laser-based experiments because of the uncontrollable sequential photodissociation producing mixed Fe(CO) intermediates.