Dialkylpalladium(II) complexes. Syntheses, characterizations, and reactions with CO, I2, and CH3I.
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概要
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The reaction of bis(acetylacetonato)palladium(II), [Pd(acac)<SUB>2</SUB>] with AlR<SUB>2</SUB>(OEt) in the presence of tertiary phosphine, L, in diethyl ether yields a series of dialkylpalladium(II) complexes, [PdR<SUB>2</SUB>L<SUB>2</SUB>], where R=Me, Et, and Pr<I><SUP>n</SUP></I>; L=PEt<SUB>3</SUB>, PPh<SUB>2</SUB>Me, and 1/2Ph<SUB>2</SUB>PCH<SUB>2</SUB>CH<SUB>2</SUB>PPh<SUB>2</SUB> (dpe). These complexes were characterized by means of elemental analysis, IR and <SUP>1</SUP>H-NMR spectra and of some decomposition reaction such as thermolysis and acidolysis. The <I>trans</I>- and <I>cis</I>-configurations of [PdMe<SUB>2</SUB>L<SUB>2</SUB>] (L=PEt<SUB>3</SUB> and PPh<SUB>2</SUB>Me, respectively) in solution were established on the basis of the <SUP>1</SUP>H-NMR spectra. The examination of <SUP>1</SUP>H-NMR spectra in the presence of tertiary phosphine suggests the ligand exchange processes promoted by the added phosphine. [PdR<SUB>2</SUB>L<SUB>2</SUB>] (L=PEt<SUB>3</SUB> and PPh<SUB>2</SUB>Me) reacted with CO in toluene to yield the quantitative amounts of the corresponding dialkyl ketones. The reactions of the complexes [PdR<SUB>2</SUB>L<SUB>2</SUB>] with iodine afforded [PdI<SUB>2</SUB>L<SUB>2</SUB>] and RI, and of [PdR<SUB>2</SUB>(dpe)] with MeI gave CH<SUB>3</SUB>H, CH<SUB>3</SUB>CH<SUB>3</SUB>, R(–H), RH, R·CH<SUB>3</SUB>, R·R, and RI together with [PdI<SUB>2</SUB>L<SUB>2</SUB>], suggesting the presence of a quadrivalent, six-coordinate intermediate palladium species.
- 公益社団法人 日本化学会の論文
著者
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Ito Takashi
Research Institute for Nanodevice and Bio Systems, Hiroshima University, Higashihiroshima, Hiroshima 739-8527, Japan
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TSUCHIYA Hirotaka
Research Center for Development of Far-Infrared Region, University of Fukui, Fukui 910-8507, Japan
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Yamamoto Akio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Tsuchiya Hirotaka
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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