Organometallic Chemistry: Recent Advances
authors Simões, M. M. Q., Santos, I. C. M. S., Neves, M. G. P. M. S., Cavaleiro, A. M. V. and Cavaleiro, J. A. S.
editors Armando J. L. Pombeiro
chapter title Functionalization of sp3 CH and sp2 carbon centres catalysed by polyoxometalates and metalloporphyrins
nationality I
abstract Transition metal substituted polyoxometalates (TMSPs) and metalloporphyrins were used as homogeneous catalysts in the oxidation of sp2 and sp3 centres of several organic compounds, in acetonitrile, using hydrogen peroxide as oxidant. The TMSPs included anions of the Keggin-type [XW11M(H2O)O39]n− (X = P, Si, B, and M = FeIII, MnIII) and of the sandwich type [M4(H2O)2(PW9O34)2]q− (M = CoII, MnII and FeIII). The metalloporphyrins were MnIII or FeIII complexes of porphyrins with different substituents at the meso and β positions, able to contribute to their stability and reactivity. The chosen substrates included cycloalkanes and cycloalkenes, alkylaromatics, monoterpenes, polycyclic aromatics and others. Both types of catalysts could be supported on derivatized silica and used as heterogeneous catalysts of some reactions. The reaction conditions and the outcome of the catalytic processes were generally different for TMSPs and metalloporphyrins, in spite of the use of the same oxidant and solvent. An account of this research developed at the University of Aveiro is presented in this chapter.
publisher Wiley-VCH
year published 2013

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