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1 Polish Journal of Chemistry

1 2002

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Synthesis, Characterization and Magnetism of Fe(II)-Pd(II0-Fe(II) Heterotrinuclear Complexes Bridged by Dioximato Groups

Li Y., Yan C. -W., Zeng X.-C.

Polish Journal of Chemistry

2002

Vol. 76 / nr 5

645-652

Three new Fe(II)-Pd(II)-Fe(II) heterotrinuclear complexes with dioximato-bridge have been synthesized and identified as [Fe2Pd(_-FD)2(Me2-bpy)4]SO4 (1), [Fe2Pd(_-FD)2(Me2-phen)4]SO4 (2) and [Fe2Pd(_-FD)2(Me-phen)4]SO4 (3); where (_-FD)2_ represents _-furildioximato; Me2-bpy, Me2-phen and Me-phen denote 4,4_-dimethyl-2,2_-bipyridine; 2,9-dimethyl-1,10-phenanthroline (Me2-phen) and 5-methyl-1,10-phenanthroline (Me-phen). Based on elemental analyses, molar conductance measurements, IR and electronic spectral studies, these complexes are proposed to have extended dioximato-bridged structures and to consist of two iron(II) ions and a palladium(II) ion, in which the central palladium(II) ion has a square-planar environment and the end capped two iron(II) ions have a distorted octahedral environment. The magnetic properties of complexes [Fe2Pd(_-FD)2(Me2-bpy)4]SO4 (1) and [Fe2Pd(_-FD)2(Me2-phen)4]SO4 (2) were investigated over the 4.2~300Krange and correspond to what is expected for an antiferromagnetic Fe(II)-Fe(II) pair with SFe(II) = 2 and SPd(II) = 0 (Pd2+ is a diamagnetic in a square-planar environment) local spins. The exchange integral (J) was evaluated as J = _2.89 for (1) and J = _3.16 for (2) based on the spin Hamiltonian operator, _ _ _ H = JS S 1 2 _ _ 2 .