Preparation and stereochemistry of cobalt(III) complexes containing 2,11-diphenyl-5,8-diaza-2,11-diphosphadodecane or (4S,9S)-4,9-dimethyl-2,11-diphenyl-5,8-diaza-2,11-diphosphadodecane, (C6H5)(CH3)PCH2CHRNHCH2CH2NHCHRCH2P(CH3)(C6H5) (R=H or CH3).

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概要

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• New quadridentate ligands having two chiral phosphorus donor atoms, 2,11-diphenyl-5,8-diaza-2,11-diphosphadodecane (mp-PNNP) and (4<I>S</I>,9<I>S</I>)-4,9-dimethyl-2,11-diphenyl-5,8-diaza-2,11-diphosphadodecane (<I>SS</I>(C)-mp-PNNP), and their cobalt(III) complexes, <I>trans</I>-[CoCl<SUB>2</SUB>(mp- or <I>SS</I>(C)-mp-PNNP)]<SUP>+</SUP> and <I>cis</I>β-[Co(acac)(mp- or <I>SS</I>(C)-mp-PNNP)]<SUP>2+</SUP> (acac=2,4-pentanedionate ion) were prepared and characterized. For both mp- and <I>SS</I>(C)-mp-PNNP, the dichloro and acac complexes formed three and four isomers, respectively, which were separated by column chromatography or fractional crystallization. No <I>cis</I>α-acac complex was yielded. The acac complexes of <I>SS</I>(C)-mp-PNNP formed a <I>Λ</I>-isomer stereoselectively. The absolute configurations of the phosphorus donor atoms in the <I>SS</I>(C)-mp-PNNP complexes were assigned on the basis of the <SUP>1</SUP>H NMR and CD spectra. It was shown that the phosphorus donor atoms at chemically unequivalent coordination positions in <I>cis</I>β-[Co(acac)(<I>SS</I>(C)-mp-PNNP)]<SUP>2+</SUP> give remarkably different vicinal effects on the CD spectra.

著者

• Kashiwabara Kazuo

  Department Of Chemistry Faculty Of Science Nagoya University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Atoh Masamichi

  Department of Chemistry, Faculty of Science, Nagoya University

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