The binuclear diphosphine bridged monocarbonyl compound [Ni(CO)]2(DPPA)3 has been obtained by reaction of Ni(CO)4 with bis(diphenylphosphino)acetylene (DPPA) under mild conditions and by displacement of π-cyclopentadienyl groups from [π-C5H5Ni(CO)]2 at room temperature. The latter reaction suggests a possible route to other monocarbonyl nickel phosphine compounds not available by direct reaction of Ni(CO)4 with phosphines. The preparation and characterization of the binuclear compounds [Ni(CO)2]2(DPPA)2, [Ni(CO)3]2(DPPA), and (π-C5H5NiI)2(DPPA) are also described.