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Photoactive metal carbonyl complexes bearing N-heterocyclic carbene ligands: synthesis, characterization, and viability as photoredox catalysts
journal contribution
posted on 2023-05-21, 05:26 authored by Meiqiong TangMeiqiong Tang, Cameron, L, Eve PolandEve Poland, Yu, LJ, Moggach, SA, Rebecca FullerRebecca Fuller, Huang, H, Sun, J, Stuart ThickettStuart Thickett, Massi, M, Coote, ML, Curtis HoCurtis Ho, Alexander BissemberAlexander BissemberThis 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.
Funding
Australian Research Council
History
Publication title
Inorganic ChemistryVolume
61Issue
4Pagination
1888-1898ISSN
0020-1669Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
© 2022 American Chemical SocietyRepository Status
- Restricted