Palladium-carbon σ-bonded complexes bearing diphosphazane and diphosphazane monosulphide ligands^†

Abstract

The reactions of the diphosphazanes and diphosphazane monosulphides, Ph₂P(E)N(R)PPh₂ [E = lone pair, R = CHMe₂ (<b>1</b>); E = lone pair, R = (<i>S</i>)-*CHMePh (<b>2</b>); E = S, R = CHMe₂ (<b>3</b>); E = S, R = (<i>S</i>)-*CHMePh (<b>4</b>)] with [PdMeCl(COD)] yield the neutral chelate complexes of the type [PdMe{ҡ²-Ph₂P(E)N(R)PPh₂}Cl] (<b>5</b>,<b>6</b>, <b>8</b> and <b>9</b>). The reactions of <b>1-3</b> with

chlorobridged cyclometallated palladium azobenzene dimmers, [Pd {(C₆H₃-R'-4)-N=N-(C₆H₄-R' -4)(μ-Cl)]₂ (Rʹ = H or OC₆H₁₃) in the presence of NH₄PF₆ yield cationic cyclopalladated complexes, [{ҡ²-(C₆H₃- R'-4)- N =N-(C₆H₄-R'-4)} Pd { ҡ²- Ph₂P(E)N(R) PPh₂}](PF₆) (<b>10-15</b>). The molecular structure of [Pd{ҡ²-(C₆H₃-OC₆H₁₃-4)-N = N-(C₆H₄-OC₆ H₁₃-4)} {ҡ²-Ph₂P(S)N(CHMe₂)PPh₂}](PF₆) (<b>15</b>) has been determined by X-ray diffraction; the palladium bound carbon atom occupies the <i>trans</i> position with respect to the sulphur atom of the chelated diphosphazane monosulphide ligand.