Hybrid ligands: synthesis, characterization and co-ordinative properties of a mixed phosphine–β-ketophosphorus ylide

Abstract

Direct C-phosphination at the methyl carbon of the keto-stabilized ylide MeC(O)CH=PPh₃ was achieved using 2 equivalents of LiBu and 1 equivalent of PPh₂Cl. The structure of the resultant phosphine–phosphorus ylide, Ph₂PCH₂C(O)CH=PPh₃, was shown by an X-ray diffraction study to comprise a 1 : 1 mixture of two rotamers built around the CH₂–C(O) axis, the C(=O)CH=PPh₃ moiety of both conformers adopting a cisoid form. A rotational barrier of 10 kJ mol^-1 between the two isomers was found using molecular-mechanics simulation. Oxidation of the ylide with sulfur resulted in quantitative formation of the corresponding phosphine sulfide Ph₂P(S)CH₂C(O)CH=PPh₃. By treating 2 equivalents of Ph₃P=CHC(O)CH₂PPh₂ (L) with [{Pd(η³-C₃H₄Me-2)Cl} ₂], the P-monodentate complex [PdCl(η³-C₃H₄Me-2)L] 1 was formed quantitatively. Reaction of 2 equivalents of L with [{PdCl(C₆H₄CH₂NMe₂- o)}₂] in tetrahydrofuran afforded, in quantitative yield, the stable cationic complex [Pd(C₆H₄CH₂NMe₂-o) L]Cl 2 where the hybrid ligand is P,O-bonded to the palladium, thus illustrating the nucleophilic character of the oxygen atom of the ylide. The BF₄^- analogue of the latter complex, 3, prepared in order to exclude counter-anion effects, was obtained by treating 1 with AgBF₄. The nickel complexes [Ni(η⁵-C₅Ph₅)L]X (X = I 4 or Br 5), in which the ligand is bound as in 1 and 2, were obtained by treating the corresponding [Ni(η⁵-C₅Ph₅)X(CO)] complexes with the ylide L.

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