The reactions of carbon monoxide with series of dirhenium species [Re2Cl4(PMe2Ph)4]n+ (n = 0, 1, 2) possessing rheniumrhenium bond orders of 4, 3.5 and 3
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abstract
The complexes [Re2Cl4(PMe2Ph)4](PF6),n, where n = 1, 1 or 5, which possess ReRe multiple bonds of orders 3, 3.5 and 4, respectively, react with carbon monoxide in 2-methoxyethanol to afford the reductive cleavage product ReCl(CO)3(PMe2Ph)2 in high yield. In other solvents (ethanol and toluene), these reactions are complicated by competing side reactions which can result in redox chemistry at the dirhenium units without the incoporation of CO into the products. The reactions in ethanol and toluene lead to the formation of Re2Cl5(PMe2Ph)3, Re2Cl6(PMe2Ph)2, trans-ReCl4(PMe2Ph)2, ReCl(CO)2(PMe2Ph)3 and/or ReCl3(CO)(PMe2Ph)3, in addition to ReCl(CO)3(PMe2Ph)2, depending upon the reaction conditions. The electrochemical properties of the carbonyl containing prosducts ReCl(CO)2(PMe2Ph)3, ReCl(CO)3(PMe2Ph)2 and ReCl3(CO)2(PMe2Ph)3, as well as those of the previuosly described rhenium(II) dicarbonyl complex ReCl2(CO)2(P-n-Pr3)2, have been studied using the cyclic voltammetry technique. 1984.
