Two new mononuclear nonheme manganese(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Mn(bpc)Cl(H(2)O)] (1) and [Mn(Me(2)bpb)Cl(H(2)O)]⋅CH(3)OH (2), were prepared and characterized. Complex 2 has also been characterized by X-ray crystallography. Magnetic measurements revealed that the complexes are high spin (S = 5/2) Mn(III) species with typical magnetic moments of 4.76 and 4.95 μ(B), respectively. These nonheme Mn(III) complexes efficiently catalyzed olefin epoxidation and alcohol oxidation upon treatment with MCPBA under mild experimental conditions. Olefin epoxidation by these catalysts is proposed to involve the multiple active oxidants Mn(V)=O, Mn(IV)=O, and Mn(III)-OO(O)CR. Evidence for this approach was derived from reactivity and Hammett studies, KIE (k(H)/k(D)) values, H(2)(18)O-exchange experiments, and the use of peroxyphenylacetic acid as a mechanistic probe. In addition, it has been proposed that the participation of Mn(V)=O, Mn(IV)=O, and Mn(III)-OOR could be controlled by changing the substrate concentration, and that partitioning between heterolysis and homolysis of the O-O bond of a Mn-acylperoxo intermediate (Mn-OOC(O)R) might be significantly affected by the nature of solvent, and that the O-O bond of the Mn-OOC(O)R might proceed predominantly by heterolytic cleavage in protic solvent. Therefore, a discrete Mn(V)=O intermediate appeared to be the dominant reactive species in protic solvents. Furthermore, we have observed close similarities between these nonheme Mn(III) complex systems and Mn(saloph) catalysts previously reported, suggesting that this simultaneous operation of the three active oxidants might prevail in all the manganese-catalyzed olefin epoxidations, including Mn(salen), Mn(nonheme), and even Mn(porphyrin) complexes. This mechanism provides the greatest congruity with related oxidation reactions by using certain Mn complexes as catalysts.

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Fluorescent organic molecules that respond to changes in the Fe2+ concentration with selectivity to other abundant di-valent metal ions will offer the ability to understand the dynamic fluctuations of the Fe 2+ ion in interesting media. The use of 6-Br-ppmbi, derived from 2-pyridin-2-yl-benzimidazole, for metal ion-selective fluorescence recognition was investigated. Screening of the main group and transition metal ions showed exclusive selectivity for Fe 2+ ions even in the presence of competing metal ions. In addition, the requirement for low concentrations of probe molecules to detect certain amounts of Fe 2+ ions make this sensor unique compared to previously reported Fe 2+ ion sensors.

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