Preparation and properties of cobalt(III)-1,2-bis(dimethylphosphino)ethane (dmpe) complexes of the [Co(L)(dmpe)2]n+ type.

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概要

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• Seven new cobalt(III)–phosphine complexes of the type [Co(L)(dmpe)<SUB>2</SUB>]<SUP><I>n</I>+</SUP> were prepared from <I>trans</I>-[Co(Cl or Br)<SUB>2</SUB>(dmpe)<SUB>2</SUB>]<SUP>+</SUP>, where dmpe denotes (CH<SUB>3</SUB>)<SUB>2</SUB>PCH<SUB>2</SUB>CH<SUB>2</SUB>P(CH<SUB>3</SUB>)<SUB>2</SUB>, and L is C<SUB>2</SUB>O<SUB>4</SUB><SUP>2−</SUP>, NH<SUB>2</SUB>CH<SUB>2</SUB>COO<SUP>−</SUP>(gly), NH<SUB>2</SUB>CH(CH<SUB>3</SUB>)COO<SUP>−</SUP>(ala), (C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>NCS<SUB>2</SUB><SUP>−</SUP>(dtc), (NCS<SUP>−</SUP>)<SUB>2</SUB>, (NCO<SUP>−</SUP>)<SUB>2</SUB>, or (CN<SUP>−</SUP>)<SUB>2</SUB>. Reactions of <I>cis</I>-[CoCl<SUB>2</SUB>(dmpe)<SUB>2</SUB>]<SUP>+</SUP> with X<SUP>−</SUP> (X<SUP>−</SUP>=CN<SUP>−</SUP>, NCS<SUP>−</SUP>, and NCO<SUP>−</SUP>) yielded only <I>trans</I>-[CoX<SUB>2</SUB>(dmpe)<SUB>2</SUB>]<SUP>+</SUP>. Qualitative stabilities of the complexes containing a bidentate ligand in aqueous solution were found to decrease in the order L=CH(CH<SUB>3</SUB>CO)<SUB>2</SUB><SUP>−</SUP>(acac), C<SUB>2</SUB>O<SUB>4</SUB><SUP>2−</SUP>, dtc>CO<SUB>3</SUB><SUP>2−</SUP>>>gly, ala>NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>(en); the complexes containing O or S donor atoms are thermally more stable than those containing an amino donor group. The d–d absorption bands of the complexes were assigned by comparing the spectra with those of related Co(III)–phosphine and -en complexes. The IR and visible absorption spectra of the NCS<SUP>−</SUP> and NCO<SUP>−</SUP> complexes indicate an N coordination mode of these ambidentate ligands.

• 公益社団法人 日本化学会の論文

著者

• Kashiwabara Kazuo

  Department Of Chemistry Faculty Of Science Nagoya University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Ohishi Tomoji

  Department of Chemistry, Faculty of Science, Nagoya University

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• タイトル無し
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