The synthesis of the two novel diphosphine compounds 1,2-bis(3-(diphenylphosphino)-4-methoxyphenyl)benzene (1; Terphos), and 1,2-bis(2-diphenylphosphino)benzene (2), both derived from a terphenyl backbone structure, are described. Straightforward synthetic routes have been employed to obtain these ligands in good yields from cheap starting materials. The coordination of ligands 1 and 2 with PtCl2(cod) has been studied by NMR spectroscopy, and the X-ray crystal structures of the resulting complexes 4 and 5 were determined. The P-31 NMR spectra of the mononuclear products demonstrate solely cis coordination for both bidentate ligands, with corresponding coupling constants J(Pt-P) of 3810 Hz (CiS-[PtCl2(1)], complex 4) and 3712 Hz (cis-[PtCl2(2)1, 5). The bite angles P-1-Pt-P-2 were 98.74 and 105.89 degrees, respectively, in the distorted square-planar complexes. The new diphosphines have been applied in the platinum/tin-catalyzed hydroformylation of 1-octene, and both ligands give active and selective platinum catalysts.