Manganese(III) complexes with MnIIIN3O3(S=2) co-ordination by sexidentate schiff-base ligands: synthesis, spectra and electrochemistry

Ramesh, Krishnamoorthi ; Bhuniya, Debnath ; Mukherjee, Rabindra Nath (1991) Manganese(III) complexes with MnIIIN3O3(S=2) co-ordination by sexidentate schiff-base ligands: synthesis, spectra and electrochemistry Journal of the Chemical Society, Dalton Transactions (11). pp. 2917-2920. ISSN 0300-9246

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/1991...

Related URL: http://dx.doi.org/10.1039/DT9910002917

Abstract

Complexes of high-spin manganese(III)(μeff= 4.79-5.30 at 298 K) with a closely related group of sexidentate Schiff-base ligands have been prepared and their solution properties thoroughly investigated. The brown to green crystalline complexes display ligand-to-metal charge-transfer transitions in the range 330-400 nm in addition to a crystal-field transition in the range 560-600 nm. The solution stereochemistry has been determined by paramagnetically shifted 1H NMR spectroscopy. Unlike the C3 symmetry in the solid-state structure, in solution the MnIIIN3O3 co-ordination sphere is severely distorted (≈C1 symmetry). Cyclic voltammetric studies in dimethylformamide solution reveal an irreversible MnIII-MnII couple [Epc in the range -0.62 to -0.05 V vs. saturated calomel electrode (SCE)] and a quasi-reversible MnIV-MnIII couple (Ef in the range +0.42 to +0.86 V vs. SCE).

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