Bis(diphenylphosphino)amid-komplexe des platins, palladiums und nickels. Kristallstruktur des N-methylierungsprodukts {CH3N[(C6H5)2P]2}2Pd2+ 2SO3F−

Abstract Reaction of lithiated bis(diphenylphosphino)amine, [(C 6 H 5 ) 2 P] 2 N − Li + , with K 2 PtCl 4 or PdCl 2 (in the presence of trimethylphosphine) yields the homoleptic bis[bis(diphenylphosphino)amide] complexes I and II, respectively. With NiCl 2 /(CH 3 ) 3 P the chloro-bridged dinuclear complex III is obtained. A symmetrical bonding of the Ph 2 P-·N-·PPh 2 anion to the metal through the phosphorus atoms is indicated for these diamagnetic, deep-yellow (I, II) or red (III) complexes by 31 P NMR spectroscopy ( J (PtP) 1812 Hz for I). I and II are dissolved in CF 3 COOH with protonation at the nitrogen atoms to give bis(diphenylphosphino)amine complexes IV and V, respectively ( J (PtP) 2080 Hz for IV). IV and V are 1:2 electrolytes in CH 3 NO 2 . Methylation of I-III with CH 3 OSO 2 F leads to the bis(diphenylphos-phino)methylamine complexes VI-VIII, of which the palladium compound VII has been structurally characterized by single crystal X-ray diffraction. VII contains a planar CNP 2 PdP 2 NC skeleton and is thus based on planar ligand arrays both at Pd and at the two N atoms.