Amidate-bridged Pt III dinuclear complexes [Pt 2 (NH 3 ) 4 (Am) 2 (H 2 O) 2 ] 4+ (Am ) amidate ligand) catalyze oxidation of olefins in acidic aqueous solution. Linear olefins are oxidized to ketones, whereas cyclic olefins are oxidized to epoxides. GC-MS analysis of the oxidation products obtained from the reaction in H 2 18 O showed that the oxygen atoms in the products are exclusively from water, suggesting that the reaction mechanism is basically similar to that of the Wacker reaction. In accordance with this mechanism, pivalamidate-bridged Pt III complex [Pt III 2 (NH 3 ) 4 ((CH 3 ) 3 CCONH) 2 (H 2 O) 2 ] 4+ has been found to react with olefins to give alkyl complexes. Reactions with 4-penten-1-ol and ethylene glycol vinyl ether in acidic aqueous solution gave [Pt III 2 (NH 3 ) 4 ((CH 3 ) 3 CCONH) 2 (CH 2 CH(CH 2 ) 3 O)](NO 3 ) 3 ‚H 2 O (7) and [Pt III 2 (NH 3 ) 4 ((CH 3 ) 3 CCONH) 2 (CH 2 CHO)]-(NO 3 ) 3 ‚H 2 O (9), respectively. The two compounds have been structurally confirmed by X-ray diffraction analysis and 1 H, 13 C, and 195 Pt NMR spectroscopy. The 1 H NMR of 9 shows that both π-and σ-complexes exist in equilibrium in D 2 O, although the X-ray structure is close to the σ-complex. High electrophilicity of the R-carbon atoms of the compounds has been shown in the reactions with OH -. The above reactions with olefins can be a general route to prepare dimeric Pt III -alkyl complexes.

The first olefin epoxidation by water oxygen is reported. The reaction is catalyzed by platinum blue complexes and is the first example that water oxygen atom is introduced into epoxides in catalytic or stoichiometric reaction.

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