The meso and rac forms of the tetraphosphine ligand bis[(diphenylphosphinoethyl)phenylphosphino]methane, Ph 2 PCH 2 CH 2 PPhCH 2 PPhCH 2 CH 2 PPh 2 (DPPEPM), have been separated and found to react with 2 equiv of [PtCl 2 (cod)] or [PtMe 2 (cod)] to generate bimetallic complexes of the form [Pt 2 X 4 (μ-DPPEPM)]. When [PtClMe(cod)] is treated with the tetraphosphine followed by TlPF 6 , the chloride-bridged species [Pt 2 Me 2 (μ-Cl)(μ-DPPEPM)]PF 6 is obtained. The solid state structures of [Pt 2 X 4 (μ-meso-DPPEPM)] (X=Cl, Me) are reported, along with preliminary studies of some hydrogenation reactions catalyzed by the bimetallic derivatives.