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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

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Monodentate phosphine substitution in [Pd(κ³-dppf)(PR₃)][BF₄]₂ (dppf = 1,1'-bis(diphenylphosphino)ferrocene)

K D Cabrera¹, A T Rowland, J M Szarko

¹Department of Chemistry, Lafayette College, Easton, PA 18042, USA. nataroc@lafayette.edu.

Dalton Transactions (Cambridge, England : 2003)

|March 8, 2017

Abstract:

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 κ³ 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(κ³-dppf)(PPh₃)]²⁺. A series of related compounds, [Pd(κ³-dppf)(P(p-C₆H₄R)₃)]²⁺ (R = OCH₃, CH₃, F and CF₃), has been synthesized and characterized. The X-ray crystal structure of [Pd(dppf)(P(p-C₆H₄F)₃)][BF₄]₂ was determined. Electrochemical and computational studies indicate that the electron donor ability of the P(p-C₆H₄R)₃ ligands influences the properties of these compounds. Substitution reactions of the P(p-C₆H₄R)₃ ligands have been examined, and, in general, the more electron donating P(p-C₆H₄R)₃ ligands completely replace the less electron donating ones. The kinetics of the reaction of [Pd(κ³-dppf)(P(p-C₆H₄F)₃)]²⁺ with P(p-C₆H₄OCH₃)₃ 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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