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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 Bissember
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.

Funding

Australian Research Council

History

Publication title

Inorganic Chemistry

Volume

61

Issue

4

Pagination

1888-1898

ISSN

0020-1669

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

© 2022 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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