Oxochloride Complexes of Rhenium

Attempts to prepare rhenium hexachloride by the method described by Colton (2) have been unsuccessful. The products of the reaction were always impure rhenium oxotetrachloride and rhenium pentachloride. A compound of rhenium(VI), ReOCl4OPCl3, is shown to have a structure analogous to that of rhenium(V) ions [ReOX4.L]− in which the ligands are in a pseudooctahedral arrangement with L trans to the oxo-group (3). Reactions of ReOCl4 and ReOCl4-OPCl3 with pyridine and 2,2′-dipyridyl are described, and a scheme is proposed for the reactions of the products. Two stable complexes of perrhenyl chloride with the above amines have been obtained.