Ligand design for electrochemically controlling stoichiometric and catalytic reactivity of transition metals

Alan M. Allgeier, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

197 Scopus citations


Chemists have several tools at their disposal for studying and subsequently controlling reactivity. Recently, redoxactive ligands were utilized in novel ways to control the reactivity of transition metal complexes. Several redoxactive ligands undergo stable and reversible changes in oxidation state, which allows one to tune the electron richness of the ligand and the bound metal. In this contribution we present an overview of redox-active ligands, which have been categorized into three classes based on their mode of reactivity control. In addition, specific examples are presented which demonstrate the utility of redox-active ligands for controlling metal-ligand binding constants and both stoichiometric and catalytic reactions involving transition metals. In some cases, these oxidation state dependent changes in reactivity can be quite significant, and alter reaction rates by several orders of magnitude and ligand binding constants by many orders of magnitude. Further development of redox-active ligands will be anchored upon a firm understanding of the factors that influence the charge-dependent behavior of transition metal complexes of these ligands. Perspectives on the future direction of research in this area are presented, in particular with respect to the interest in new redox-active groups and potential applications in redox-switchable catalysis and materials for the separation of molecules.

Original languageEnglish (US)
Pages (from-to)894-908
Number of pages15
JournalAngewandte Chemie - International Edition
Issue number7
StatePublished - 1998


  • Cyclic voltammetry
  • Homogeneous catalysis
  • Ligand effects
  • Redox chemistry
  • Substituent effects

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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