Selectivity in reductive elimination from dialkyl(aryl)palladium(IV) complexes, and the observation of benzyl halide transfer from palladium(IV) to palladium(II) : The X-ray structure of methyl(phenyl)(2,2'-bipyridyl)-palladium(II)

The first arylpalladium(IV) complexes, [PdXMePhR(bpy)] (bpy = 2,2'-bipyridyl), have been isolated upon oxidative addition of methyl iodide or benzyl bromide to the organopalladium(II) reagent [PdMePh(bpy)]. These dialkyl(aryl)palladium(IV) complexes undergo reductive elimination in solution at ca. 0°C: [PdBrMePh(CH2Ph)(bpy)] decomposes quantitatively into [PdBr(CH2Ph)(bpy)] and toluene whereas [PdIMe2Ph(bpy)] gives ethane and toluene in 4:1 ratio together with the corresponding complexes [PdIR(bpy)] (R = Me or Ph). The reaction of methyl iodide with [PdMePh(tmeda)] at 0°c yields ethane and [PdIPh(tmeda)] without detection of a palladium(IV) intermediate. No reaction of [PdMePh(tmeda)] with benzyl bromide was observed. The first demonstration that organic groups can be transferred from palladium(IV) to palladium(II) is reported. The molecular structure of [PdMePh(bpy)] in the solid state has been determined

Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts

Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C6[C6H3(CH2Y)2-3,5]6 (10, Y = NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C6[C6H3(CH2Br)2-3,5]6 (9). The hexakis(pincer) palladium(II) complexes C6[(PdX)-4-C6H2(CH2Y)2-3,5]6 (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3[Br-4-C6H3(CH2NMe2)2-3,5]3-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis[(dimethylamino)methyl]acetophenone (19). Reaction of 20 with Pd(dba)2 yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2NMe2)2-3,5]3-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D3 symmetry and a fixed bromine-bromine distance of 17.4573(4) Å, approximately forming a triangle with a height of 15.2 Å. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y' pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y' PdII complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl -cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N'-type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P'- and S,C,S'-pincer complexes (1d, Y = PPh2; 1e, Y = SPh). The nanosize cationic tri-N,C,N' PdII complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 × 10-6 s-1 for 1a vs k = 232 × 10-6 s-1 for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor