Manganese() complexes, [MnL 2 ] [H 2 L = MeC(OH)᎐ ᎐ CHCMe᎐ ᎐ NN᎐ ᎐ C(SH)SR (R = Me 1a or CH 2 Ph 1b)] and manganese() complexes, [Mn(O 2 CMe)L] 1c or [Mn(acac)L] 1d [acac = acetylacetonate; H 2 L = PhCH(OH)CPh᎐ ᎐ NN᎐ ᎐ C(SH)SCH 2 Ph] have been synthesized and characterized. The Schiff-base ligands which are derived from an aliphatic carbonyl function, favour the facile oxidation of manganese-() to -() under ambient conditions.The structure determination of 1a showed that the molecule is octahedral with the two equivalent tridentate ligands spanned meridionally. The EPR spectrum of 1a with a strong but structured signal at g ≈ 4.0 and a weak one at g ≈ 2.0 implies a large zero-field splitting, but the spectral profile differed from an ideal axial form. All the complexes exhibited reversible or quasi-reversible Mn IV -Mn III redox couples in their cyclic voltammograms at potentials commensurate with the nature of the substituents in the appropriate ligands. A reasonable basis is suggested by which one may predict whether a particular ligand will stabilize manganese-(), -() or -() in an aerobic medium.
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