Photoactive Metal Carbonyl Complexes Bearing N-Heterocyclic Carbene Ligands: Synthesis, Characterization, and Viability as Photoredox Catalysts

Meiqiong Tang, Lee Cameron, Eve M. Poland, Li Juan Yu, Stephen A. Moggach, Rebecca O. Fuller, Hai Huang, Jianwei Sun, Stuart C. Thickett, Massimiliano Massi, Michelle L. Coote, Curtis C. Ho, Alex C. Bissember

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)1888-1898
Number of pages11
JournalInorganic Chemistry
Volume61
Issue number4
DOIs
Publication statusPublished - 31 Jan 2022
Externally publishedYes

Keywords

  • Photoactive
  • Metal
  • Carbonyl
  • N-Heterocyclic
  • Carbene
  • Ligands
  • Photoredox
  • metals

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