Ultrafast Studies Of Organometallic Photochemistry PDF Download

Ultrafast time-resolved infrared spectroscopy provides a powerful tool for studying the photochemistry of organometallic complexes. The studies described herein focus on the mechanisms of photochemically initiated organometallic reactions with a particular emphasis on two topics: the role of spin states and spin state changes in organometallic reactions, and the primary photochemical dynamics of complexes containing metal-metal bonds (e.g. transition metal dimers and clusters). Many of these studies seek to uncover trends in reactivity based on the spin states of organometallic reaction intermediates, with the goal of being able to offer some level of predictive insight into the reactivity of complexes as classified by their spin multiplicity. The reactivity of various coordinatively unsaturated reaction intermediates are studied with respect to bond activation, electron transfer, excited state photoisomerization, and other classes of reactions important to organometallic catalysis. A second focus, which shares some degree of overlap with the topic of spin state changes, is the primary photochemistry of complexes containing metal-metal bonds. Several of the studies reported herein use time-resolved infrared spectroscopy to examine the primary photochemical processes occurring upon excitation of transition metal dimers and clusters, and often spin state changes also found to play an important role. Results of computational chemistry calculations are frequently used to facilitate interpretation of the experimental results by computation of structures, relative energies, infrared spectra, and spin-orbit coupling for the complexes studied experimentally. Additional studies outside these two primary areas of focus also investigated the ring-slippage of cyclopentadienyl ligands and the CO-delivery properties of a popular CO-Releasing Molecule.