A new catalytic reaction of the etherification of alcohols in the system ROH-PtCl 4 2− has been observed. At 70 °C in the presence of catalytic amounts of chloride complexes of platinum(II) methanol gave dimethyl ether. Methyl tert-butyl ether and di-tert-butyl ether were formed analogously from a mixture of methanol and tert-butanol. In the reaction with ethanol the products were diethyl ether and a π-ethylene complex of platinum(II). It is suggested that the step-wise mechanism includes the oxidative addition of the alcohol with the intermediate formation of an alkyl complex of platinum(IV), the decomposition of which by reductive elimination under the influence of a second molecule of alcohol or an alkoxide anion gives an ether and regenerates the catalyst, a chloride complex of platinum(II).
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Mitchenko, S.A., Vdovichenko, A.N., Bezbozhnaya, T.V. et al. Formation of Ethers from Alcohols with Chloride Complexes of Platinum(II) as Catalysts. Theor Exp Chem 41, 203–206 (2005). https://doi.org/10.1007/s11237-005-0041-9
- chloride complexes of platinum(II)
- oxidative addition
- reductive elimination