Reaction of [(h5-C5Me5)(CO)2MP(SiMe3)2] (M = Fe, Ru, Os) with RPCl2 (I; R = 2,4,6-tert-Bu3C6H2) in THF at 20 Deg afforded the novel diphosphenyl complexes (E)-(h5-C5Me5)(CO)2MP:PR. Only the Fe and Ru derivs. could be isolated from the reaction mixt. as ocher-yellow or orange-yellow solids. The corresponding Os deriv. was trapped as its Ni(CO)3 complex. Similarly, stable (h5-C5H5)(CO)(PPh3)FeP:PR was generated from (h5-C5H5)(CO)(PPh3)FeP(SiMe3)2 and I. The novel coordination compds. were characterized by elemental anal. and spectroscopic methods (IR, 1H, 13C, and 31P NMR, and mass spectroscopy). The mol. structure of (h5-C5Me5)(CO)2FeP:PR was established by a complete single-crystal diffraction study.