Synthesis, structure, and magnetism of binuclear Cu(II)Cu(II), Cu(II)Ni(II), and Ni(II)Ni(II) complexes doubly bridged by oxymate groups.
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Binuclear complexes, [Cu(L)Cu(L<SUP>′</SUP>)(H<SUB>2</SUB>O)<SUB>2</SUB>]X<SUB>2</SUB> (H<SUB>2</SUB>L=3,3<SUP>′</SUP>-trimethylenedinitrilobis(2-butanoneoxime) (H<SUB>2</SUB>dopn) or 3,3′-ethylenedinitrilobis(2-butanoneoxime) (H<SUB>2</SUB>doen); L′=2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen); X=ClO<SUB>4</SUB> or NO<SUB>3</SUB>), [Ni(dopn)Cu(bpy)(H<SUB>2</SUB>O)](ClO<SUB>4</SUB>)<SUB>2</SUB>, and [Ni(dopn)Ni(bpy)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>2</SUB>, have been prepared and characterized. The structure of [Cu(dopn)Cu(phen)(CH<SUB>3</SUB>OH)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>2</SUB> (di-methanol adduct) has been determined by single crystal X-ray method. The Cu(dopn) molecule coordinates to the second copper(II) ion through the deprotonated oximate oxygens to afford a binuclear structure doubly bridged by the oximate groups in the cis arrangement. The binuclear cation is bent at the oxymate oxygens with a dihedral angle of 26.7(2)°. The binuclear copper(II) complexes show a characteristic visible band of significant intensity (ε 2700–2900 dm<SUP>3</SUP> mol<SUP>−1</SUP>cm<SUP>−1</SUP>) near 22000 cm<SUP>−1</SUP> and a strong intramolecular antiferromagnetic spin-exchange interaction. The exchange integrals (<I>J</I>) are evaluated to be −413.3–−433.0 cm<SUP>−1</SUP>. The magnetic moment (per molecule) of the nickel(II)–copper(II) complex is 1.80 μ<SUB>B</SUB> at room temperature and the moment of the binuclear nickel(II) complex is 2.94 μ<SUB>B</SUB>, demonstrating that the Ni(dopn) entity of these complexes is diamagnetic.
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関連論文
- Synthesis, structure, and magnetism of binuclear Cu(II)Cu(II), Cu(II)Ni(II), and Ni(II)Ni(II) complexes doubly bridged by oxymate groups.
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