Palladium diphenyl-2-pyridylphosphine complexes

The stoichiometric reaction of diphenyl-2-pyridylphosphine (Ph2PC5H4N-2) and palladium(II) acetate afforded the palladium(I) dimer [Pd2(µ-Ph2PC5H4N)2(OAc)2] 1. Attempts to isolate the monomer, [Pd(µ-Ph2PC5H4N)2(OAc)2], from 2∶1 stoichiometry reactions (Ph2PC5H4N∶Pd), resulted only in the isolation of 1. When >3 mole equivalents of Ph2PC5H4N were used the zerovalent palladium complex [Pd(Ph2PC5H4N)3] was isolated. Other palladium(I) dimers with carboxylic or sulfonic anionic ligands have been prepared by a metathesis reaction of the co-ordinated acetates. The complexes 1 and [Pd2(µ-Ph2PC5H4N)2(O2CCF3)2] 2 have been structurally characterised as head-to-tail dimers. The mononuclear complex [Pd(Ph2PC5H4N)2(O2CCF3)2] has been obtained by reaction of Ph2C5H4N with [Pd(CH3CN)2(O2CCF3)2]. Complex 1 reacts with dimethyl acetylenedicarboxylate to give [Pd2(µ-Ph2PC5H4N)2(OAc)2(µ-MeO2CCCCO2Me)], while attempts to isolate an A-frame carbonyl complex were unsuccessful.

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