First structural characterization of a delocalized, mixed-valent, triangular Cu37+ species: chemical and electrochemical oxidation of a CuII3(mu3-O) pyrazolate and electronic structure of the oxidation product.
The chemical or electrochemical one-electron oxidation of the all-CuII complex [Cu3(mu3-O)(mu-pz)3X3]2- leads to its formally CuII2CuIII analogue (pz = pyrazolato anion; X = Cl- and PhCOO-). The X-ray single-crystal structure and density functional theory analysis of the latter agree in revealing the delocalized nature of its mixed-valent Cu3(7+) core.
Mezei
Gellert
G
Department of Chemistry, University of Puerto Rico, San Juan, Puerto Rico 00931-3346.
McGrady
John E
JE
Raptis
Raphael G
RG
D003300:Copper; D018360:Crystallography, X-Ray; D004563:Electrochemistry / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011720:Pyrazoles / Q000737:chemistry*
C511539:(mu3-oxo)tris(mu-pyrazolate)tris(benzoate)tricopper(II); D009942:Organometallic Compounds; D011720:Pyrazoles; D003300:Copper