Modification of the multistep synthesis of the previously described bis[5-(diphenylphosphanyl)pyrazol-1-yl)]methane (bppzm, 1) produces the novel diphosphane (diphenylphosphanyl)-[5-(diphenylphosphanyl)pyrazol-1-yl](pyrazol-1-yl)methane (p4m, 2). Treatment of this ligand with [MCl2(PhCN)2] (M = Pd, Pt) or [M(COD)(THF)2]BF4 (M = Rh, Ir) produces [MCl2(p4m)] (M = Pd 3, Pt 4) or [M(COD)(p4m)]BF4 (M = Rh 5, Ir 6) complexes, which chelate in a P,P-bidentate fashion. Sulfidation of bppzm and p4m produces the disulfidophosphanes bppzmS2 (7) and p4mS2 (8). Treatment of 7 and 8 with [PdCl2(PhCN)2] produces [PdCl2(bppzmS2)] (9) and [PdCl2(pmS2)] (10), respectively, in which ligands 7 and 8 act in an N,N-bidentate chelate fashion. In contrast, ligand 8 reacts with [Rh(COD)(THF)2]BF4 to produce [Rh(COD)(p4mS2)]BF4, where ligand 7 acts in a dynamic S,S-chelate fashion. The activity of some of these complexes in the catalytic hydrogenation of olefins is reported and the single-crystal X-ray structures of 4, 8, and 9 have been obtained. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)