Inter‐ and Intramolecular Electron Transfer in Copper Complexes: Electronic Entatic State with Redox‐Active Guanidine Ligands. Issue 55 (6th September 2017)

• Record Type: Journal Article
• Authors: Schrempp, David F.; Leingang, Simone; Schnurr, Martin; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans‐Jörg
• Is Part Of: Chemistry. Volume 23:Issue 55(2017)
• Page Start: 13607
• Page End: 13611
• Publication Date: 2017-09-06
• Subjects: copper -- electron transfer -- entatic state -- redox active ligands -- π-donor ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201703611
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Fast and efficient electron transfer in blue copper proteins is realized by a structural harmonization between the Cu I and Cu II complex pair ("entatic state" model). Herein, we present now a Cu I /Cu II complex pair with redox‐active guanidine ligands showing almost perfect match between both redox states. By modifying the ligand electron donor strength, the redox chemistry of the copper complex can be controlled to be either metal‐centered or to cross the borderline to ligand‐centered. This work is the first systematic study of complexes with redox‐active ligands within the concept of the entatic state. Abstract : π‐Donor strength makes it possible : Using redox‐active guanidine ligands, Cu II complexes with a coordination sphere much closer to tetrahedral than square‐planar are realized, being ideal entatic state models (see scheme).