Miscellaneous complexes

The uranyl-ion-catalysed oxidation of ascorbic acid has been shown to proceed via a path first-order with respect to substrate, catalyst, molecular oxygen, and hydrogen (or deuterium) ion concentrations. In the presence of any excess of oxygen, the rate law may be expressed in the form 

The triprotonated species, UOa HsA Oa is considered to involve two protons on the oxo-oxygens of the uranyl ion with the other on one of the ascorbate oxygen donor atoms. The rate-determining process is the 

Preliminary results of the reaction between vanadium(iii)-tetrasulpho-phthalocyanine complex with oxygen have been reported these data were compared with those obtained for the corresponding reaction of the hexa-aquo complex ion. The oxidation of methyl ethyl ketone by oxygen in the presence of Mn -phenanthroline complexes has been studied Mn complexes were detected as intermediates in the reaction and the enolic form of the ketone hydroperoxide decomposed in a free-radical mechanism. In the oxidation of 1,3,5-trimethylcyclohexane, transition-metal [Cu , Co , Ni , and Fe ] laurates act as catalysts and whereas in the absence of these complexes there is pronounced hydroperoxide formation, this falls to a low stationary concentration in the presence of these species, the assumption being made that a metal-hydroperoxide complex is the initiator in the radical reaction. In the case of nickel, the presence of such hydroperoxides is considered to stabilise the Ni 02 complex. Ruthenium(i) chloride complexes in dimethylacetamide are active hydrogenation catalysts for olefinic substrates but in the presence of oxygen, the metal ion is oxidised to ruthenium(m), the reaction proceeding stoicheiometrically. Rhodium(i) carbonyl halides have also been shown to catalyse the oxidation of carbon monoxide to carbon dioxide under acidic conditions  

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Phosphine Complexes and Miscellaneous Complexes 9.10.4.3.1 Phosphine complexes... 

VI. Miscellaneous Complexes, and Complexes in Which an Olofinic Ligand Has... 

Spectral data for miscellaneous complexes are available in the references cited in Table 8.31. The covalency parameters of some complexes are given in Table 8.50 (see Appendix). 

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