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Photoactive metal carbonyl complexes bearing N-heterocyclic carbene ligands: synthesis, characterization, and viability as photoredox catalysts




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Abstract
This report details the synthesis and characterization of a small family of previously unreported, structurally related chromium, molybdenum, tungsten, manganese, and iron complexes bearing N-heterocyclic carbene and carbonyl supporting ligands. These complexes have the general form [ML(CO)3X] or [ML(CO)3], where X = CO or Br and L = 1-phenyl-3-(2-pyridyl)imidazolin-2-ylidene. Where possible, the solid-state, spectroscopic, electrochemical, and photophysical properties of these molecules were studied using a combination of experiment and theory. Photophysical studies reveal that decarbonylation occurs when these complexes are exposed to ultraviolet light, with the CO ligand being replaced with a labile acetonitrile solvent molecule. To obtain insights into the potential utility, scope, and applications of these complexes in visible-light-mediated photoredox catalysis, their capacity to facilitate a range of photoinduced reactions via the reductive or oxidative functionalization of organic molecules was investigated. These chromium, molybdenum, and manganese catalysts efficiently facilitated atom-transfer radical addition processes. In light of their photolability, these types of catalysts may potentially allow for the development of photoinduced reactions involving less conventional inner-sphere electron-transfer pathways.
Item Type: | Article |
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Authors/Creators: | Tang, M and Cameron, L and Poland, EM and Yu, LJ and Moggach, SA and Fuller, RO and Huang, H and Sun, J and Thickett, SC and Massi, M and Coote, ML and Ho, CC and Bissember, AC |
Keywords: | N-heterocyclic carbenes, transition metals, photoredox catalysis |
Journal or Publication Title: | Inorganic Chemistry |
Publisher: | Amer Chemical Soc |
ISSN: | 0020-1669 |
DOI / ID Number: | https://doi.org/10.1021/acs.inorgchem.1c02964 |
Copyright Information: | © 2022 American Chemical Society |
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