New Organometallic Palladium(II) Complexes Containing P∩N Ligands – Synthesis, Characterization and X-ray Structure

Abstract

New neutral organometallic palladium(II) complexes, [PdPhI(PNMe2)] (1), [PdPhI(PC=NMe)] (2), [PdPhI(PC=NEt)] (3), and [PdMeCl(PNMe2)] (4), {PNMe2 means N,N‐dimethyl‐2‐(diphenylphosphanyl)aniline; PC=NMe means N‐[2‐(diphenylphosphanyl)benzylidene]‐N‐methylamine; PC=NEt means N‐[2‐(diphenylphosphanyl)benzylidene]‐N‐ethylamine} have been synthesized by oxidative addition of PhI to [Pd(dba)2] in the presence of the P∩N ligand (1–3), or by substitution reaction on [PdMeCl(COD)] with PNMe2 (4). Cationic σ‐organometallic species [PdR(PPh3)(P∩N)]+ are obtained upon treating complexes of the type [PdRX(P∩N)] with PPh3 and AgCF3SO3 and consist predominantly of the trans‐P,P isomer in CDCl3 solution, as shown by NMR spectroscopic studies. The cationic η3‐allyl complex [Pd(η3‐all)(PNMe2)]PF6 has also been prepared and characterized, both in solution and in the solid state. Compounds [PdPhI(PNMe2)] (P21/n), [PdPhI(PC=NMe)] (P1¯), [PdPhI(PC=NEt)] (P1¯), and [Pd(η3‐all)(PNMe2)]PF6 (P1¯) have been authenticated by X‐ray analysis