Structural, magnetic and spectroscopic characterization of novel di-.MU.-carboxylato-bridged binuclear copper(II) complexes with 1,10-phenanthroline.

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概要

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• Bis(μ-carboxylato-<I>O</I>,<I>O</I>′)-diaquabis(1,10-phenanthroline)dicopper(II) dinitrate tetrahydrates, [Cu(RCOO)(phen)(H<SUB>2</SUB>O)]<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>·4H<SUB>2</SUB>O, where R=H, CH<SUB>3</SUB>, and (CH<SUB>3</SUB>)<SUB>3</SUB>C, were prepared and characterized by elemental analyses, electronic spectra, magnetic susceptibilities, and X-ray structure analysis. The magnetic susceptibility data conform to the usual dimer equation. The −2<I>J</I> values are 125 cm<SUP>−1</SUP> for formate, 86 cm<SUP>−1</SUP> for acetate, and 99 cm<SUP>−1</SUP> for 2,2-dimethylpropanoate. The crystal structures of [Cu(HCOO)(phen)(H<SUB>2</SUB>O)]<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>·4H<SUB>2</SUB>O (<B>1</B>) and [Cu(CH<SUB>3</SUB>COO)(phen)(H<SUB>2</SUB>O)]<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>·4H<SUB>2</SUB>O (<B>2</B>) were determined by the single-crystal X-ray diffraction method. The crystallographic data are: Compound <B>1</B>, monoclinic, <I>I</I>2⁄<I>a</I>, <I>a</I>=18.850(2), <I>b</I>=9.775(2), <I>c</I>=17.752(2) Å, β=99.03(1)°, <I>V</I>=3230.4(8) Å<SUP>3</SUP>, <I>Z</I>=4, <I>R</I>=0.055 for 2511 observed unique reflections; Compound <B>2</B>, monoclinic, <I>C</I>2⁄<I>c</I>, <I>a</I>=18.563(4), <I>b</I>=14.272(5), <I>c</I>=14.126(3) Å, β=106.72(2)°, <I>V</I>=3584(2) Å<SUP>3</SUP>, <I>Z</I>=4, <I>R</I>=0.082 for 2092 reflections. The complexes consist of dimeric [Cu(RCOO)(phen)(H<SUB>2</SUB>O)]<SUB>2</SUB><SUP>2+</SUP>)] cations with five-coordinated copper ions linked by two carboxylato ions in a syn-syn bridging arrangement. The Cu···Cu distances are 3.103(2) Å for <B>1</B> and 3.063(3) Å for <B>2</B>.

• 公益社団法人 日本化学会の論文

著者

• Tokii Tadashi

  Department Of Chemistry And Applied Chemistry Facukty Of Science And Engineering Saga University

• Nakashima Michio

  Department Of Chemistry Faculty Of Science And Engineering Saga University

• Muto Yoneichiro

  Department Of Chemistry Faculty Of Science And Engineering Saga University

• Saito Yoshihiko

  Department Of Cardiology Juntendo University School Of Medicine

• OHBA SHIGERU

  Deparment of Biology, Faculty of Science, Tokyo Metropolitan University

• Watanabe Naofumi

  Department of Chemistry, Faculty of Science and Engineering, Saga University

• Morooka Mitsuo

  Department of Chemistry, Faculty of Science and Technology, Keio University

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