A Paramagnetic Copper(III) Complex Containing an Octahedral CuIII S6 Coordination Polyhedron

Carsten Krebs; Thorsten Glaser; Eckhard Bill; Thomas Weyhermüller; Wolfram Meyer-Klaucke; Karl Wieghardt

doi:10.1002/(SICI)1521-3773(19990201)38:3<359::AID-ANIE359>3.0.CO;2-5

A Paramagnetic Copper(III) Complex Containing an Octahedral Cu^III S₆ Coordination Polyhedron

Angew Chem Int Ed Engl. 1999 Feb 1;38(3):359-361. doi: 10.1002/(SICI)1521-3773(19990201)38:3<359::AID-ANIE359>3.0.CO;2-5.

Authors

Carsten Krebs¹, Thorsten Glaser¹, Eckhard Bill¹, Thomas Weyhermüller¹, Wolfram Meyer-Klaucke², Karl Wieghardt¹

Affiliations

¹ Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-3063951.
² EMBL-Outstation Hamburg, Gebäude 25A, Notkestrasse 85, D-22603 Hamburg (Germany).

PMID: 29711643
DOI: 10.1002/(SICI)1521-3773(19990201)38:3<359::AID-ANIE359>3.0.CO;2-5

Abstract

Only the second octahedral, paramagnetic copper(III) complex (S=1) has now been synthesized and characterized. Six thiolato bridging ligands in the heterotrinuclear species [LCo^III Cu^III Co^III L](ClO₄ )₃ ⋅2 Me₂ CO (L=1,4,7-tris(4-tert-butyl-2-sulfidobenzyl)-1,4,7-triazacyclononane) stabilize this rare electron configuration. A section of the structure of the reduced form (Cu^II , S=½) is shown. XAS, EXAFS, and EPR spectroscopy prove unambiguously that the one-electron oxidation to the copper(III) is metal- rather than ligand-centered.

Keywords: Cobalt; Copper; EXAFS spectroscopy; S ligands.