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A Paramagnetic Copper( III ) Complex Containing an Octahedral Cu III S 6 Coordination Polyhedron
Author(s) -
Krebs Carsten,
Glaser Thorsten,
Bill Eckhard,
Weyhermüller Thomas,
MeyerKlaucke Wolfram,
Wieghardt Karl
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990201)38:3<359::aid-anie359>3.0.co;2-5
Subject(s) - electron paramagnetic resonance , octahedron , copper , crystallography , paramagnetism , extended x ray absorption fine structure , chemistry , x ray absorption spectroscopy , metal , ligand (biochemistry) , inorganic chemistry , crystal structure , absorption spectroscopy , nuclear magnetic resonance , physics , condensed matter physics , biochemistry , receptor , organic chemistry , quantum mechanics
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](ClO 4 ) 3 ⋅2 Me 2 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.