A novel representative of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide containing Cl-substituent in the meta- position of the aryl groups was obtained with a high yield based on the reaction of (1,2,3-triarylcyclopropenyl)tributylphosphonium bromide and sodium polyphosphides. Further reaction of sodium 3,4,5-tri(3-chlorophenyl)-1,2-diphosphacyclopentadienide with [FeCp(η6-C6H5CH3)][PF6] complex gives a new 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene. The electrochemical properties of 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene were studied and compared with 3,4,5-tris(4-chlorophenyl)-1,2-diphosphaferrocene. It was found that the position of the chlorine atom in the aryl fragment has a influence on the reduction potential of 1,2-diphosphaferrocenes, while the oxidation potentials do not change..