Transition metal complexes of the pyridylphosphine ligand o-C₆H₄(CH₂PPy₂)₂

The synthesis and coordination behaviour of the pyridylphosphine ligand o-C₆H₄(CH₂PPy₂)₂ (Py = 2-pyridyl) are reported. The phosphine selenide was synthesised and the ¹J_PSe value of 738 Hz indicates the phosphorus atoms have a similar basicity to PPh₃. The ligand reacts with platinum(ii) and palladium(ii) complexes to give simple diphosphine complexes of the type [MX₂(PP)] (M = Pt, X = Cl, I, Me, Et; M = Pd, X = Cl, Me). When the ligand is reacted with chloromethyl(hexa-1,5-diene)platinum the [PtClMe(PP)] complex results, from which a series of unsymmetrical platinum complexes of the type [PtMeL(PP)]⁺ (L = PPh₃, PTA, SEt₂ and pyridine) can be made. This enabled the comparison of the cis and trans influences of a range of ligands. The following cis influence series was compiled based on ³¹P NMR data of these complexes: Py ≈ Cl > SEt₂ > PTA > PPh₃. Reaction of [PtClMe(PP)] with NaCH(SO₂CF₃)₂ and carbon monoxide slowly formed an acyl complex, where the CO had inserted in the Pt-Me bond. Attempts to achieve P,P,N chelation, through abstracting the chloride ligand in [PtClMe(PP)], were unsuccessful. When the ligand reacted with platinum(0), palladium(0) and silver(i) complexes the bis-chelated complexes [M(PP)₂] (M = Pt, Pd) and [Ag(PP)₂]⁺ were formed respectively. Reaction of the ligand with [Ir(COD)(μ-Cl)]₂ formed [IrCl(PP)(COD)]. When the chloride ligand was abstracted, the pyridyl nitrogens were able to interact with the iridium centre facilitating the isomerisation of the 1,2,5,6-η⁴-COD ligand to a 1-κ-4,5,6-η³-C₈H₁₂ ligand. The X-ray crystal structure of [Ir(1-κ-4,5,6-η³-C₈H₁₂)(PPN)]BPh₄ confirmed the P,P,N chelation mode of the ligand. In solution, this complex displayed hemilabile behaviour, with the pyridyl nitrogens exchanging at a rate faster than the NMR time scale at room temperature.