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The ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) is commonly employed in a variety of catalytic systems. There are a variety of coordination modes known for dppf, the least studied being the κ coordination mode, in which both phosphorus atoms and the iron atom of dppf interact with another metal center. One such compound is the previously reported [Pd(κ-dppf)(PPh)]. A series of related compounds, [Pd(κ-dppf)(P(p-CHR))] (R = OCH, CH, F and CF), has been synthesized and characterized. The X-ray crystal structure of [Pd(dppf)(P(p-CHF))][BF] was determined. Electrochemical and computational studies indicate that the electron donor ability of the P(p-CHR) ligands influences the properties of these compounds. Substitution reactions of the P(p-CHR) ligands have been examined, and, in general, the more electron donating P(p-CHR) ligands completely replace the less electron donating ones. The kinetics of the reaction of [Pd(κ-dppf)(P(p-CHF))] with P(p-CHOCH) indicate that the reaction proceeds through a dissociative mechanism, contrary to the associative substitutions prevalent in square planar palladium(ii) chemistry.

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