New bis(phosphine-amide) ligands: Oxidation, coordination and supramolecular chemistry

作者：Xu Qiu; Zhang Fenbao; Jennings Michael C; Puddephatt Richard J^*

来源：Polyhedron, 2017, 131: 46-51.

DOI：10.1016/j.poly.2017.04.028

• Bis(phosphine-amide)
• Platinum
• Gold
• Supramolecular polymer
• Coordination polymer

The synthesis of four new bis(phosphine-amide) ligands E{NHC()-4-C6H4PPh2)(2), E = 1,4-C6H4, 1,3-C6H4, 1,4-C6H4(CH2)(2) or 1,4-C6H10, is reported along with a preliminary study of their properties. The ligands are slowly oxidized in solution to give the corresponding phosphine oxides, and they form complexes with gold(I) with bridged structures [Au2Cl2{mu-E(NHC(=O)-4-C6H4PPM2)] or large macrocyclic structures [Au-2{mu-E(NHq=O)-4-C6RIPPh2)(2)}(2)]X-2, with X- = triflate or nitrate. A macrocyclic platinum (II) complex cis,cis-[Pt2Cl4{mu-1,4-C6H4 (NHC(=O)-4-C6H4PPh2)(2))(2)], was prepared but an attempt to isolate a related cationic complex [Pt-2(dPPP)(2){mu-E(NHC(=O)-4-C6H4PPh2)(2)}](OTf)(4) led to ligand hydrolysis, with formation of the unusual phosphine-carboxylate bridged complex [Pt-2(dPPP)(2)(mu-O2C-(4)-C6H4PPh2)(2)}] (OTf)(2), dppp = Ph2P(CH2)(3)PPh2. The amide groups of the bis(phosphine-amide) ligands take part in hydrogen bonding, which may lead to self-assembly of more complex structures.

• 出版日期2017-7-27