The relative stability of palladium superoxido complexes, formed via o-or n-type co-ordination of a superoxide ion in monomeric and trimeric palladium species, has been investigated by CNDO-S2, a semi-empirical quantum chemical SCF-m.0. method. The CN DO-S2 method has been adapted to calculate the energetic and geometric properties of transition-metal compounds. A n-type co-ordination for 0,is calculated t o be most stable for monomeric palladium species, while o-type co-ordination is favoured for trimeric species. Experimental data on the reactivity of palladium superoxido complexes towards the epoxidation of simple alkenes are in agreement with the results of CNDO-S2 calculations.
Formation of two types, type I and type II of Pd superoxo complexes in the reactions of Pd(II) acetate, propionate, trifluoroacetate, and bis(acetylacetonate) and of Pd(PPh3)4 with H2O2 or KO2 in various solvents are detected by EPR.
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