A double-oxidation deprotonation sequence transforms the title hydride complexes into the corresponding unsaturated cations [M2Cp2 (μ-PPh2)(CO) 4]+, which can also be obtained through a two-step oxidation of the title carbonylates. These reactions involve respectively the 33-electron binuclear radicals [M2Cp2 (μ-H)(μ-PPh2)(CO) 4]+ and [M2Cp2 (μ- PPh2)(CO) 4] as intermediates, as shown in the scheme.