Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Abstract

Photochemistry has evolved into a powerful tool for the highly selective generation of reactive intermediates in inorganic and organometallic chemistry. This review examines the state of the art in the examination of mechanisms of photochemical reactions utilizing techniques such as frozen matrices and fast time‐resolved methods. The application of photochemistry to the preparation of dihydrogen, alkane, and noble gas intermediates is reviewed along with the significance of these intermediates in the understanding of the mechanism of oxidative addition processes. Experiment and theory of charge transfer phenomena are extensively discussed along with the application of these processes to semiconductor and biochemical studies. Applications of photocrystallography to the examination of linkage isomers and very short‐lived excited state species are reviewed. Finally, a number of examples of the application of photochemical reactions, such as the photolysis of Fisher carbene species to generate ketenelike intermediates, to synthesis are discussed. The literature is reviewed to the end of 2003.

Photochemistry of (η4-diene)Ru(CO)3Complexes as Precursor Candidates for Photoassisted Chemical Vapor Deposition

“…While there may be some MLCT character to the observed transitions based on the population of CO π* orbitals from metal d origins, the experimental data are not consistent with MLCT transitions ( vide infra ). We suspect that the majority of the photochemistry occurs from LF bands, consistent with the observation of photochemical ligand loss from 2a – 5a . , …”

“…We suspect that the majority of the photochemistry occurs from LF bands, consistent with the observation of photochemical ligand loss from 2a−5a. 31,32 Absorption Spectra. Based on the experimental UV/vis spectrum of (COT)Fe(CO) 3 , 22 its lowest energy excitation band was assigned to be a d−d LF transition.…”

“…These results are consistent with the photochemistry at the lowest-energy excitation band most likely occurring from an LF transition, which is in agreement with previously reported data on photosubstitution. 31,32 Although CO dissociation after population of the CO π* orbital of (η 3 -allyl)Ru(CO) 3 X 20 has been reported, photochemistry by dissociation from MLCT states 33−35 is not common.…”