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Keywords:

  • Cyanides;
  • Non-innocent ligands;
  • Organometallic chemistry;
  • Oxido ligands

Abstract

This essay for EurJIC's cluster issue on cooperative and redox non-innocent ligands introduces the reader to redox-active ligands, which range from the small archetypical NO+/•/– and O20/•–/2–systems via the classical 1,4-dihetero-1,3-diene chelates (e.g. α-diimine, dithiolene, or o-quinone redox series) to π-conjugated macrocycles. The increased attention paid recently to the redox activity of ligands in coordination chemistry has now prompted wider successful searches, resulting in the establishing of less-conventional examples such as cyanide, carbon monoxide, thioethers, or acetylacetonate derivatives as non-innocently behaving ligands. By considering situations with significantly covalent metal–ligand bonding, the cases of metal–oxo, metal–hydrido, and organometallic compounds will also be addressed, with a perspective on how pervasive non-innocent ligand behavior is. The materials and reactivity potential of redox-active ligands will be pointed out.