257602-60-1Relevant articles and documents
Halide-Bridged Palladium(II) Dimers of Orthometalated (S)-(+)-N,N-Dimethyl-α-methylbenzylamine and (S)-(+)-N,N-Dimethyl[1-(2-naphthyl)ethyl]amine: Solution and Solid-State Structures and Reactions with 3,4-Dimethyl-1-phenylphosphole and Allyldiphenylphosphine
Guel, Nizamettin,Nelson, John H.
, p. 91 - 104 (2008/10/08)
Activation thermodynamics for the cis - trans isomerization of the chloride-, bromide-, and iodide-bridged palladium(II) dimers of orthometalated (S)-(+)-N,N-dimethyl-α-methylbenzylamine (TMBA) and (S)-(+)-N,N-dimethyl[1-(2-naphthyl)-ethyl]amine (TMNA) have been determined by variable-temperature 1H NMR spectroscopy. The chloride-bridged dimers are cleaved regioselectively by 3,4-dimethyl-1-phenylphosphole (DMPP) and allyldiphenylphosphine (ADPP) to form the mononuclear products {Pd(C6H4CH(Me)NMe2(R3P)Cl} and {Pd(C10H6CH(Me)NMe2(R3P)Cl} (R3P = DMPP, ADPP), with the phosphine exclusively trans to nitrogen. The chloride-bridged dimers react with NaPF6 or AgClO4, DMPP, and CH3CN to produce {Pd(C6H4CH(Me)NMe2(DMPP)(CH3CN)}X and {Pd(C10H6CH(Me)NMe2(DMPP)(CH3-CN)}X (X = PF6-, ClO4-). They react with NaPF6 or AgClO4 and excess DMPP to form [Pd-(DMPP)4](X)2 (X = PF6-, ClO4-). When X = PF6-, this complex undergoes two thermal [2+2] dimerizations of the coordinated DMPP ligands in the solid state to form {Pd(DMPP2-[2+2])2}(PF6)2. The complex {Pd(C10H6CH(Me)NMe2(DMPP)Cl} reacts with AgClO4 and ADPP at 75°C to form an unusual chloride-bridged tetrapalladium(II) macrocycle that contains a novel tridentate ligand with bridging phosphide and terminal R3P and C(-) donors. New complexes were characterized by elemental analyses, physical properties, infrared spectroscopy, polarimetry, and 1H, 1H{31P}, 13C{1H}, and 31P{1H} NMR spectroscopy and in most cases by X-ray crystallography.
