Dinaionic Ligand Complexes, K_2[CuL^n] and K_2[NiL^n] (n = 1, 2; H_4L^1=1, 2-Bis(2-hydroxybenzamido)ethane, H_4L^2=1, 2-Bis(2-hydroxybenzamido)benzene), and Their Dinuclear Cu(II)-Cu(II) and Ni(II)-Cu(II) Complexes

Access this Article

Search this Article

Author(s)

Abstract

Copper(II) and nickel(II) complexes with tetraanionic quadridentate ligands, K<sub>2</sub>[CuL<sup><i>n</i></sup>] and K<sub>2</sub>[NiL<sup><i>n</i></sup>] (<i>n</i> = 1, 2), have been prepared. We examined whether or not they can function as “ligand complexes”, where H<sub>4</sub>L<sup>1</sup> = 1,2-bis(2-hydroxybenzamido)ethane and H<sub>4</sub>L<sup>2</sup> = 1,2-bis(2-hydroxybenzamido)benzene. One of the ligand complexes, K<sub>2</sub>[NiL<sup>1</sup>]·2dmf·2H<sub>2</sub>O, crystallizes in the monoclinic space group <i>P</i>2<sub>1</sub>/<i>n</i> with the cell dimensions of <i>a</i> = 15.34(8), <i>b</i> = 18.99(8), <i>c</i> = 18.86(5) Å, <i>β</i> = 100.2(3), <i>V</i> = 5406 Å<sup>3</sup>, and <i>Z</i> = 8. The <i>ligand complex</i> assumes a unique one-dimensional structure consisting of {[KO<sub>3</sub>][K(NiL<sup>1</sup>)O]}<sub><i>n</i></sub> as the repeating unit, where each K<sup>+</sup> ion is surrounded octahedrally by six oxygen atoms with the distances of 2.672(2)—2.866(9) Å and all the oxygen atoms act as bridging group to K<sup>+</sup> ion. Each of the precursor complexes can function as an electrically dianionic bidentate “ligand complex” and reacts with Cu(II) ion and terminal capping ligand (cap) such as 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), ethylenediamine (en), and 1,3-diaminopropane (tn) to give di-<i>μ</i>-phenoxo-bridged dinuclear Cu(II)–Cu(II) and Ni(II)–Cu(II) complexes with the general formula of [(Cu or Ni)L<sup><i>n</i></sup>Cu(cap)]. The molar electrical conductivities of the dinuclear complexes measured in the DMF or DMSO solutions are essentially zero, indicating that the dinuclear structures are preserved in the solutions. The electrochemical measurements for a series of [CuL<sup>2</sup>Cu(cap)] (cap = bpy, phen, tn) demonstrated that the Cu(II/III) redox process of the {CuL<sup>2</sup>} site exhibits more positive potential (−0.04 — −0.09 V) than that of the mononuclear precursor complex (−0.288 V). One of the dinuclear complexes, [CuL<sup>2</sup>Cu(phen)(DMSO)], crystallizes in the orthorhombic space group <i>Pna</i>2<sub>1</sub> with the cell dimensions of <i>a</i> = 19.702(3), <i>b</i> = 15.847(3), <i>c</i> = 9.652(2) Å, <i>V</i> = 3013 Å<sup>3</sup>, and <i>Z</i> = 4. The complex consists of a discrete di-<i>μ</i>-phenoxo-bridged dinuclear structure, in which two copper(II) ions assume a square planar and square pyramidal coordination geometry and the bridging core of Cu<sub>2</sub>O<sub>2</sub> is unequivalent, as found in the distances of Cu(1)–O(1) = 1.924(4) Å, Cu(1)–O(2) = 1.908(4) Å, Cu(2)–O(2) = 1.964(4) Å and Cu(2)–O(1) = 2.249(4) Å. The magnetic susceptibility is well reproduced with the antiferromagnetic coupling parameter of <i>J</i> = −82 cm<sup>−1</sup> by the Bleaney–Boweres equation.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 70(8), 1851-1858, 1997-08-15

    The Chemical Society of Japan

References:  43

  • <no title>

    KAHN O.

    Molecular Magnetism, 1993

    Cited by (69)

  • <no title>

    GATTESCHI D. ed

    Magnetic Molecular Materials 198, 1991

    Cited by (1)

  • <no title>

    KAHN O.

    Struct. Bonding 67, 89, 1987

    Cited by (2)

  • <no title>

    GLEIZES A.

    J. Am. Chem. Soc. 103, 7373, 1981

    Cited by (6)

  • <no title>

    NARUTA Y.

    Angew. Chem. Int. Ed. Engl. 33, 1839, 1994

    Cited by (9)

  • <no title>

    OKAWA H.

    Inorg. Chem. 32, 2949, 1939

    Cited by (1)

  • <no title>

    COSTES J. -P.

    J. Chem. Soc., Dalton Trans. 1989, 1017

    Cited by (4)

  • <no title>

    MATSUMOTO N.

    J. Chem. Soc. Dalton Trans 1988, 1021

    Cited by (5)

  • <no title>

    O'CONNOR C. J.

    Inorg. Chem. 18, 1077, 1979

    Cited by (2)

  • <no title>

    JOURNAUX Y.

    J. Am. Chem. Soc. 107, 6305, 1985

    Cited by (1)

  • <no title>

    BREWER G. A.

    Inorg. Chem. 26, 1529, 1987

    Cited by (1)

  • <no title>

    JOURNAUX Y.

    Inorg. Chem. 25, 439, 1985

    Cited by (1)

  • <no title>

    JOURNAUX Y.

    Inorg. Chem. 25, 4063, 1985

    Cited by (1)

  • <no title>

    GRUBER S. J.

    Inorg. Nucl. Chem. Lett. 3, 495, 1967

    Cited by (1)

  • <no title>

    GRUBER S. J.

    J. Inorg. Chem. 7, 268, 1967

    Cited by (1)

  • <no title>

    GRUBER S. J.

    Inorg. Nucl. Chem. Lett. 4, 107, 1968

    Cited by (1)

  • <no title>

    GRUBER S. J.

    Inorg. Nucl. Chem. Lett. 30, 1805, 1968

    Cited by (1)

  • <no title>

    SINN E.

    Coord. Chem. Rev. 4, 391, 1969

    Cited by (5)

  • <no title>

    BEAR C. A.

    J. Chem. Soc., Dalton Trans. 1974, 1059

    Cited by (2)

  • <no title>

    EPSTEIN J. M.

    J. Chem. Soc., Dalton Trans. 1974, 1954

    Cited by (2)

  • <no title>

    FUKUHARA C.

    Bull. Chem. Soc. Jpn. 62, 3939, 1989

    Cited by (2)

  • <no title>

    OJIMA H.

    Nippon Kagaku Zasshi 88, 329, 1967

    Cited by (1)

  • <no title>

    ANSON F. C.

    J. Am. Chem. Soc. 109, 2974, 1987

    Cited by (2)

  • <no title>

    PERRIN D. D.

    Purification of Laboratory Chemicals, 1988

    Cited by (16)

  • <no title>

    LINDOY L. F.

    J. Chem. Educ. 49, 117, 1972

    Cited by (3)

  • <no title>

    BOUDREAUX E. A.

    Theory and Applications of Molecular Paramagnetism, 491-495, 1976

    Cited by (3)

  • <no title>

    HAI-FU Fan

    Structure Analysis Programs with Intelligent Control, 1991

    Cited by (4)

  • <no title>

    DEBAERDEMAEKER T. ed.

    MULTAN88, 1988

    Cited by (2)

  • <no title>

    Computer program for the automatic solution of crystal structures from X-ray diffraction data

    Cited by (1)

  • <no title>

    SHELDRICK G. M.

    SHELXS-86, 1986

    Cited by (5)

  • <no title>

    A program for X-ray crystal structure determination

    Cited by (1)

  • <no title>

    BEURSKENS P. T. ed.

    DIRDIF92, 1992

    Cited by (2)

  • <no title>

    The DIRDIF program system, Technical Report of the Crystallography Laboratory

    Cited by (4)

  • <no title>

    CREAGH D. C.

    International Tables for Crystallography C, 1992

    Cited by (4)

  • <no title>

    CROMER D. T.

    International Tables for X-Ray Crystallography IV, Table 2.2A, 1974

    Cited by (42)

  • <no title>

    teXsan : Crystal Structure Analysis Package, 1992

    Cited by (53)

  • <no title>

    GEARY W. J.

    Coord.Chem.Rev. 7, 81, 1971

    Cited by (13)

  • <no title>

    NAKAMURA M.

    Inorg. Chim. Acta 62, 201, 1982

    Cited by (1)

  • <no title>

    IZATT R. M.

    Synthetic Multidentate Macrocyclic Compounds, 1978

    Cited by (3)

  • <no title>

    CRAWFORD W. H.

    Inorg. Chem. 1976, 2107

    Cited by (1)

  • <no title>

    JULVE M.

    Inorg. Chem. 23, 3802, 1984

    Cited by (1)

  • <no title>

    BOSSEK U.

    J. Am. Chem. Soc 112, 6387, 1990

    DOI  Cited by (2)

  • <no title>

    GRUBER S. J.

    J. Chem. Phys. 49, 2183, 1968

    DOI  Cited by (2)

Codes

  • NII Article ID (NAID)
    10008921661
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4277766
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
Page Top