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

Tang, M, Cameron, L, Poland, EM, Yu, LJ, Moggach, SA, Fuller, RO ORCID: 0000-0003-3926-8680, Huang, H, Sun, J, Thickett, SC ORCID: 0000-0002-8168-3856, Massi, M, Coote, ML, Ho, CC ORCID: 0000-0002-7555-0635 and Bissember, AC ORCID: 0000-0001-5515-2878 2022 , 'Photoactive metal carbonyl complexes bearing N-heterocyclic carbene ligands: synthesis, characterization, and viability as photoredox catalysts' , Inorganic Chemistry, vol. 61, no. 4 , pp. 1888-1898 , doi: 10.1021/acs.inorgchem.1c02964.

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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
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: 10.1021/acs.inorgchem.1c02964
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© 2022 American Chemical Society

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