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Keywords:

  • Homogeneous catalysis;
  • Co­operative catalysis;
  • First-row metals;
  • Li­gand–metal cooperativity;
  • Dinuclear complexes;
  • Noninnocent ligands;
  • Hemilabile ligands

Abstract

Cooperative catalysis with first-row transition metals holds much promise for future developments regarding sustainable, selective transformations, including e.g. alkenes, dienes and a variety of small molecules such as CO2, N2 and water. This non-exhaustive analysis of the current state-of-the-art aims to give a comprehensive overview of the various design strategies and applications of first-row transition metal cooperative reactivity and to provide leads for new research initiatives in order to expand this emerging field. The main aspects covered involve bimetallic cooperativity, redox-noninnocent ligands in combination with first-row transition metal complexes, otherwise reactive or noninnocent scaffolds that can induce metal-ligand bifunctional substrate activation and the design of adaptive ligands and complexes thereof, wherein hemilability is a key factor for selective reactivity. The metals under review are primarily the late transition metals Fe, Co, Ni and Cu.