METAL CARBONYL-TRIFLUOROPHOSPHINE SYSTEMS .7. COBALT CARBONYL HYDRIDES AND PERFLUOROALKYLS

Cobalt carbonyl compounds of the type RCo(CO)4, where R is H, CF,3, C2F5, or C3F7, react readily with PF3 to yield all possible substitution compositions of the type RCO(PF3)x(CO)4-x. The hydride substitution takes place quite rapidly and spontaneously even at -20°. The perfluoroalkyls react more slowly than the hydrides, but the substitution is readily induced by ultraviolet light or slight heating and pressure. The various compositions can be isolated by gas-liquid partition chromatography. The materials are colorless or light yellow liquids, having melting points well below room temperature. Their thermal stability increases as the degree of substitution increases. The lower hydride species readily disproportionate, but the higher substitution products of the hydrides and all substituents of the alkyls can be kept chromatographically pure. The infrared spectra of these species indicate that they contain nonseparable isomers. Solvolysis studies support this hypothesis. © 1969, American Chemical Society. All rights reserved.