Exchange reactions between the alpha-zirconated phospholane 3, obtained by the addition of [Cp(2)ZrHCl](n) (2) to the dihydrophosphole 1, and dimethyl- or diphenylchlorophosphine 4a or 4b or bis(diisopropylamino)- or bis(dicyclohexylamino)phosphenium salts 5a or 5b, proceed with inversion of configuration at the alpha-substituted phospholane carbon atom and lead to diphosphines 6a,b,d,e. The optically active dihydrophosphole (R(p))-1 reacts with [Cp(2)ZrHCl](n) then diphenylchlorophosphine to give the 1,1-diphosphine 6b* isolated in the form of the optically active diphosphine disulfide (R(p))-14, which is characterized by X-ray diffraction studies (crystal data for (R(p))-14 : orthorombic, P2(1)2(1)2(1), a = 8.391(5) Angstrom, b = 10.880(3) Angstrom, c = 22.651(6) Angstrom, R = 0.038). In contrast, retention of configuration at the alpha-substituted phospholane carbon atom in 3 is observed when 3 is reacted with the chlorodiazaphospholane 4c, giving rise to the diphosphine 6c isolated in the form of the diphosphine disulfide 15. 15 is characterized by X-ray diffraction studies (crystal data for 15 : monoclinic, P2(1)/C, a = 8.243(5) Angstrom, b = 23.468(3) Angstrom, c = 9.412(6) Angstrom, R = 0.042). Comparison of the structures of 3, 6b, (R(p))-14, and 15 is done on the basis of NMR data, molecular modeling, and X-ray crystallographic studies.