Reactions of CO2 with Cu(I) Alkoxides and Amides to Give Alkylcarbonato-, μ-Carbonato-, Hydrogencarbonato-, and Carbamato-copper Complexes

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Abstract
Carbon dioxide reacts with ROCu(PPh3)2 (R=C2H5, C6H5CH2; PPh3=triphenylphosphine) to produce ROCO2Cu(PPh3)2. Hydrolysis or thermolysis of the alkylcarbonatocopper(I) complexes gives a binuclear carbonatocopper(I) complex (PPh3)2CuOCO2Cu(PPh3)2, which is further converted into a hydrogencarbonatocopper(I) complex [HOCO2Cu(PPh3)2]n by the reaction with CO2 in moist solvents. The IR spectrum of [HOCO2Cu(PPh3)2]n shows association of the HOCO2Cu(PPh3)2 units through hydrogen bonds. The IR spectrum of [HOCO2Cu(PPh3)2]n also reveals that the mode of the association depends on conditions of the crystallization of the complex. The reaction of (PPh3)2CuOCO2Cu(PPh3)2 with CH3I gives (CH3O)2CO and the reaction of [HOCO2Cu(PPh3)2]n with C6H5NH2 affords C6H5NHCO2Cu(PPh3)2 in high yields. Carbon dioxide reacts also with an amidocopper(I) complex C6H5NHCu(PPh3)2 to yield a carbamatocopper(I) complex C6H5NHCO2Cu(PPh3)2. The reaction of CH3Cu(PPh3)2(diethyl ether)0.5 with CO2 in the presence of HN(C2H5)2 affords (C2H5)2NHCO2Cu(PPh3)2. The isocyanate group of phenyl isocyanate is inserted into the C2H5O–Cu bond of C2H5OCu(PPh3)2 to give a (ethyl N-phenylcarbamato)copper complex.

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