.ETA.3-Allyl(methyl)platinum (II) complexes. Synthesis, conversion into .ETA.1-allyl complexes, and electrochemical behavior in comparison with thermolysis.

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概要

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• Complexes of the type [Pt(η<SUP>3</SUP>-allyl)Me(L)] (<B>1</B>) (allyl=C<SUB>3</SUB>H<SUB>5</SUB>, 1-MeC<SUB>3</SUB>H<SUB>4</SUB>, or 2-MeC<SUB>3</SUB>H<SUB>4</SUB>; L=tertiary phosphine) as well as [Pt(η<SUP>3</SUP>-C<SUB>3</SUB>H<SUB>5</SUB>)Bu(PPh<SUB>3</SUB>)] have been synthesized and characterized by NMR (<SUP>1</SUP>H, <SUP>13</SUP>C) and mass spectroscopy. By the reaction with bidentate tertiary phosphines (L–L), [Pt(η<SUP>3</SUP>-C<SUB>3</SUB>H<SUB>5</SUB>)Me(PPh<SUB>3</SUB>)] (<B>1b</B>) was converted into η<SUP>1</SUP>-allyl complexes of the type [Pt(η<SUP>1</SUP>-C<SUB>3</SUB>H<SUB>5</SUB>)Me(L–L)]. With PPh<SUB>3</SUB>, <I>cis</I>-[Pt(η<SUP>1</SUP>-C<SUB>3</SUB>H<SUB>5</SUB>)Me(PPh<SUB>3</SUB>)<SUB>2</SUB>] was isolated. The reaction of <B>1b</B> with neat 2,4-pentanedione (Hacac) afforded [Pt(acac)Me(PPh<SUB>3</SUB>)]. Complexes <B>1</B> thermally decompose in the solid state and in diphenylmethane solely giving propylene and methane, but the allyl-alkyl coupling reaction to form 1-butene is promoted by the addition of maleic anhydride. A similar coupling-promoting effect was observed in the electrochemical oxidation of <B>1b</B> in THF at 23°C without additive. By taking into account the one-electron oxidation and the participation of the PPh<SUB>3</SUB> ligand in its oxidation process, a possible mechanism of this electrochemically promoted coupling is proposed.

著者

• Nakamura Yukio

  Department Of Biotechnology Faculty Of Agriculture Gifu University

• Ueda Michihisa

  Department Of Electronics Osaka Electro-communication University

• Suzuki Takeshi

  Department Of Allergy And Rheumatology Graduate School Of Medicine University Of Tokyo

• Koumoto Ryuhei

  Department of Chemistry, Faculty of Science, Osaka City University

• Ueda Michihisa

  Department of Chemistry, Faculty of Science, Osaka City University

• Suzuki Takeshi

  Department of Chemistry, Faculty of Science, Osaka City University

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