Coinage metal complexes supported by a “PN3P” scaffold

Abstract

A series of monovalent group 11 complexes, [2,6-{Ph₂PNMe}₂(NC₅H₃)]CuBr 1, [2,6-{Ph₂PNMe}₂(NC₅H₃)]CuOTf 2, [2,6-{Ph₂PNMe}₂(NC₅H₃)]AgOTf 3, and [2,6-{Ph₂PNMe}₂(NC₅H₃)](AuCl)₂4, supported by a neutral PN³P ligand have been synthesized and characterized by multinuclear NMR and single crystal X-ray diffraction studies. The variation of the coordination properties were analyzed and electronic structure calculations have been carried out to provide insight on the bonding details in these complexes. The Cu(I) complexes displayed an unusual coordination geometry with a tridentate pincer ligand and an overall four coordinate trigonal pyramidal geometry. In contrast the Ag(I) analogue displayed a bidentate κ²-P,P′ ligation leaving the pyridyl-N atom uncoordinated and yielding a pyramidalized trigonal planar geometry around Ag. The bimetallic Au(I) complex completed the series and displayed a monodentate P-bonded ligand and a linear coordination geometry.