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

Citation

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, Photoactive metal carbonyl complexes bearing N-heterocyclic carbene ligands: synthesis, characterization, and viability as photoredox catalysts, Inorganic Chemistry, 61, (4) pp. 1888-1898. ISSN 0020-1669 (2022) [Refereed Article]

Copyright Statement

2022 American Chemical Society

DOI: doi:10.1021/acs.inorgchem.1c02964

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 Details

Item Type:Refereed Article
Keywords:N-heterocyclic carbenes, transition metals, photoredox catalysis
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Tang, M (Miss Meiqiong Tang)
UTAS Author:Poland, EM (Mrs Eve Poland)
UTAS Author:Fuller, RO (Dr Rebecca Fuller)
UTAS Author:Thickett, SC (Dr Stuart Thickett)
UTAS Author:Ho, CC (Dr Curtis Ho)
UTAS Author:Bissember, AC (Associate Professor Alex Bissember)
ID Code:148650
Year Published:2022
Funding Support:Australian Research Council (DP210100025)
Deposited By:Chemistry
Deposited On:2022-02-01
Last Modified:2022-04-07
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