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• W2068971512 abstract "Reaction of five 2- (arylazo)phenol ligands (abbreviated in general as Hap-R, where H stands for the phenolic proton) with [Os (bpy)2Br2] has afforded complexes of type [OsII (bpy)2 (ap-R)]+, which have been isolated as the perchlorate salts. The complexes are diamagnetic (low-spin d 6, S=0) and in acetonitrile solution shows several MLCT transitions in the visible region. Structure of the [Os (bpy)2 (ap-Me))ClO4 complex has been determined by X-ray crystallography. The 2- (arylazo)phenolate anion is coordinated to osmium as a bidentate N,O-donor forming a five-membered chelate ring and the OsN5O coordination sphere is distorted octahedral. Cyclic voltammetry shows a reversible osmium (II)–osmium (III) oxidation in the range of 0.37–0.51 V vs SCE followed by an irreversible osmium (III)-osmium (IV) oxidation in the range of 1.36–1.50 V vs SCE. These oxidation potentials are sensitive to the electronic nature of the substituent R in the 2- (arylazo)phenolate ligands. Three one-electron reductions of the coordinated bpy ligands are also displayed on the negative side of SCE below −1.0 V. Chemical or electrochemical oxidation of the [OsII (bpy)2 (ap-R)]ClO4 complexes affords brownish-yellow [OsIII (bpy)2 (ap-R)]fn2 species, which have been isolated as the perchlorate salts. These complexes are one-electron paramagnetic (low-spin d 5, S=1/2) and in acetonitrile solution show LMCT transitions in the visible region. Reduction of the brownish-yellow [OsIII (bpy)2 (ap-R)] (ClO4)2 complexes gives back the respective brown [OsII (bpy)2 (ap-R)]ClO4 complexes." @default.
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• W2068971512 date "1998-12-01" @default.
• W2068971512 modified "2023-09-26" @default.
• W2068971512 title "Chemistry of 2- (arylazo) phenolate complexes of osmium. Synthesis, structure and redox properties" @default.
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• W2068971512 doi "https://doi.org/10.1016/s0277-5387(98)00278-2" @default.
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