The coordination chemistry of the ligands dibenzyl disulfide, 1, and dibenzyl diselenide, 2, with Pd(TT) and Pt(II) has been investigated. These ligands are shown to coordinate via one or both of the donor atoms. For 1, the tendency for both chalcogens atoms to complex resulted in the unexpected trinuclear complexes (MCl(2))3(1)4, M = Pd and Pt, in which there are two different ligand types : one bridging two different metal centers using both S atoms and one acting as a terminal, single sulfur donor. One equivalent of 2 plus [Pt(mu-Cl)Cl(PMe(2)Ph)](2) gave the dinuclear compound [PtCl2(PMe(2)Ph)](2) {2}, 7, whose solid-state structure has been determined by X-ray diffraction. Crystal data for 7 : C30H36Cl4P2Pt2Se2.075CH(2)Cl(2), M = 1212.2, space group P2(1)/a, a 33.278(6) Angstrom, b = 14.056(4) Angstrom, c 17.603(3) Angstrom, beta = 104.71(2)degrees, V = 7964(3) Angstrom(3) and Z = 8. Unusual Se-77 NMR behavior has been observed in that, for the Pt-Se-77(1)(CH(2)Ph) -(77)Se(2)CH(2)Ph fragment, the coordination chemical shift for Se-77(2), not complexed, is much larger than that for Se-77(1), the coordinated ligand atom. The trans-influence for 1, as determined by P-31 NMR, is found to be similar to that of other neutral sulfur donors. (195) Pt spectra were recorded for several compounds.