Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation |
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Authors: | Kazunori Maruyama Takashi Ito Akio Yamamoto |
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Institution: | Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 227 Japan |
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Abstract: | Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR3)n to give benzoylnickel complexes, PhCONi(acac)PR3 (R = Ph, Et, cyclo-C6H11), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh3 in acetone was studied by NMR, and found to be first order in the benzoylnickel complex. |
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