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The anodic electrochemistry of 1-di-tert-butylphosphino-1′-diphenylphosphinoferrocene (dppdtbpf) was performed in methylene chloride with tetrabutlylammonium hexafluorophosphate as the supporting electrolyte. The electrochemistry is complicated by a chemical reaction after the oxidation. Three new transition metal complexes of dppdtbpf ([NiCl2(dppdtbpf)], [PtCl2(dppdtbpf)], and [Au2Cl2(dppdtbpf)]) were prepared and characterized. The electrochemistry of the three new compounds and one previously prepared compound ([PdCl2(dppdtbpf)]) was examined. In addition, the reaction of dppdtbpf with sulfur and/or selenium afforded a series of compounds containing a phosphine sulfide (dppSdtbpSf or dppdtbpSf), a phosphine selenide (dppSedtbpSef or dppdtbpSef), or both a phosphine sulfide and a phosphine selenide (dppSedtbpSf or dppSdtbpSef). These compounds were characterized by NMR, and the structures of three of the compounds were determined. Two of the structures are of the isomeric compounds, dppSdtbpSef and dppSedtbpSf, in which the sulfur and selenium atoms are switched between the two different phosphine groups. The anodic electrochemistry of these sulfur- and/or selenium-containing compounds was examined in methylene chloride. The potentials at which oxidation occurs are more positive than those of the free phosphine. Nearly all of the oxidations are complicated by at least one chemical reaction. [ABSTRACT FROM AUTHOR]