Ternary .ALPHA.-amino acid-palladium(II) complexes with ligand-ligand hydrogen bonding.

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概要

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• Histidinate(His)-containing ternary α-amino acid-palladium(II) complexes have been studied by synthetic and spectroscopic methods. The following complexes with imidazolate (im), L- and D-His, L-asparaginate (L-Asn), and L-glutaminate (L-Gln) have been isolated as crystals: [Pd(im)<SUB>2</SUB>]·0.5H<SUB>2</SUB>O; [Pd(L-His) (D-His)]·H<SUB>2</SUB>O; [Pd(L-Asn)-(L-His)]·2H<SUB>2</SUB>O; [Pd(L-Gln) (L-His)]·2H<SUB>2</SUB>O. The ternary systems involving palladium (II), L-His, and an amino acid L-AA with an OH or a CONH<SUB>2</SUB> group (AA=Asn, Gln, serinate, threoninate, or homoserinate) exhibit absorption maxima at 300–311 nm with ε 310–440 and negative and positive circular dichroism (CD) peaks at 307–328 nm and ≈300 nm, respectively. <SUP>13</SUP>C and <SUP>1</SUP>H NMR spectra gave the amounts of the <I>cis</I> and <I>trans</I> isomers of Pd(His)-(AA) in solution and confirmed that Pd(His)(AA) has an N<SUB>3</SUB>O donor set in the coordination plane. Whereas the CD magnitude additivity holds for the ternary systems Pd (L-His)(B) with B=glycinate, L-alaninate, or L-valinate and the systems with L-histidine methyl ester (L-HisOMe) and L-AA, Pd(L-HisOMe)(L-AA), the magnitudes for Pd (L-His) (L-AA) deviate significantly from those estimated on the basis of the additivity. The CD magnitude anomaly as well as the geometrical and rotational isomer populations calculated from the <SUP>1</SUP>H NMR spectra establishes the existence of the ligand-ligand interaction between the carboxylato group of His and the hydroxyl or amido group of AA in solution.

• 公益社団法人 日本化学会の論文

著者

• Odani Akira

  Faculty Of Pharmaceutical Sciences Kanazawa University

• Yamauchi Osamu

  Faculty Of Engineering Kansai University

• YAMAUCHI OSAMU

  Faculty of Pharmaceutical Sciences, Kanazawa University

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