• Gagan C Mandal

      Articles written in Journal of Chemical Sciences

    • Reactivity investigations of some chosen peroxo-vanadium(V), manganese(III) and chromium(VI) compounds

      Mihir K Chaudhurp Shiv K Chettri Gagan C Mandal Pradip C Paul Satya B Paul Pendyala Srinivas

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      An interpretative account of the results of reactions in aqueous medium of a highly peroxygenated vanadium(V) complex, K [V(O23]·3H2O, with different organic and inorganic substrates is presented. The reactions were monitored by solution EPR spectroscopy and isolation of products at different stages of the reactions. Redox reactions between diperoxide, K[VO(O2)2(H2O)] and VOSO4 were conducted. The results of the investigation suggest that secondary oxygen exchange-reaction occurs which not only depends on but also utilises the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of VOSO4.

      In an interesting reactiontris(acetylacetonato)-manganese(III), Mn(acac)3, on being reacted with a hydrogen peroxide adduct, KF·H2O2, and bpy and phen afforded crystalline [Mn(acac)2(bpy)] and [Mn(acac)2(phen)], respectively. The X-ray structural analysis of [Mn(acac)2(phen)] showed that the compound crystallised in orthorhombic space groupPbcn. The structure consists of a pseudooctahedral Mn(II) ion being bound to two acac(C5H5O2) and a phen ligand with the molecule lying on two-fold axis.

      Reactivity profiles of two new chromium(VI) reagents viz., pyridinium fluorochromate, C5H5NH[CrO3F] (PFC), and quinolinium fluorochromate C9H7NH [CrO3F] (QFC), have been presented. The compounds are capable of acting as both electron-transfer and oxygen-atom-transfer agents. The X-ray analysis of PFC crystals reveals that the compound crystallises in the orthorhombic space group CmcZ1. The structure consists of discrete pyridinium cations and CrO3 F anions with no significant hydrogen bonding. This results in total disorder of the pyridinium cation. The tetrahedral [CrO3 F] ion lies on a crystallographic mirror plane.

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