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Synthesis and characterization of μ-oxamido copper(Ⅱ)-iron(Ⅱ) heterobinuclear complexes with an antiferromagnetic exchange interaction

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Chinese Journal of Chemistry 1997年第6期15卷 504-511页

作者： YAN, Cui-Wei LI, Yan-Tuan LIAO, Dai-ZhengDepartment of Biology, Qufu Normal University, Qufu, Shandong 273165, ChinaDepartment of Chemistry, Qufu Normal University, Qufu, Shandong S73165, ChinaDepartment of Chemistry, Nankai University, Tianjin 300071, China

Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-21.9 cm-1 for 1 and J=-23.6 cm-1 for 2. These results are commensurate with antiferromagnetic interactions between adjacent metal ions within each molecule.

关键词： μ-Oxamido heterobinuclear complex Cu(Ⅱ)-Fe(Ⅱ) magnetism

Syntheses and Magnetic Properties of Cu（Ⅱ）－RE（Ⅲ） heterobinuclear complexes with N，N′－Bis（3－carboxyisalicylidene）－trimethylenediamine

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Chemical Research in Chinese Universities 1994年第3期10卷 179-184页

作者： TAO Ruo-jie, YU Zliao-wen and ZHOU Xu-ya(Departmeut of Chemistry, Henan University , Kaifeng, 475001 )JIN Dou-man(Hauau Institute of Chemistry . Zhengzhou, 450003 )LIAO Dai-zheng(Department of Chemistry , Nankai University , Tianjin, 300071)

ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.

关键词： Schiff base,Cu(Ⅱ)-RE(Ⅲ) heterobinuclear complex Variable-tem-perature magnetic susceptibility

Synthesis,characterization and reactivity of thiolate-bridged cobalt-iron and ruthenium-iron complexes

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Chinese Chemical Letters 2022年第1期33卷 217-220页

作者： Chao Guo Linan Su Dawei Yang Baomin Wang Jingping Qu State Key Laboratory of Fine Chemicals Dalian University of TechnologyDalian 116024China State Key Laboratory of Bioreactor Engineering Shanghai Collaborative Innovation Centre for BiomanufacturingFrontiers Science Center for Materiobiology and Dynamic ChemistryEast China University of Science and TechnologyShanghai 200237China

Thiolate-bridged hetero-bimetallic complexes[Cp^(*)M(MeCN)N_(2)S_(2)FeCl][PF_(6)](2,M=Ru;3,M=Co,Cp^(*)=η^(5)-C_(5)Me_(5),N_(2)S_(2)=N,N'-dimethyl-3,6-diazanonane-1,8-dithiolate)were prepared by self-assembly of dimer[N_(2)S_(2)Fe]2 with mononuclear precursor[Cp^(*)Ru(MeCN)_(3)][PF_(6)]or[Cp^(*)Co(MeCN)_(3)][PF_(6)]_(2)in the presence of CHCl_(3)as a chloride *** 2 and 3 exhibit obviously different redox behaviors investigated by cyclic voltammetry and spin density distributions supported by DFT ***,iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex *** the presence of CoCp_(2),complex 3 can undergo one-electron reduction to generate a stable formally Co^(II)Fe^(II)complex[Cp^(*)CoN_(2)S_(2)FeCl](4).Besides,the terminal chloride on the iron center in 3 can be removed by dehalogenation agent AgPF_(6)or exchanged with azide to afford the corresponding complexes[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(MeCN)][PF_(6)]_(2)(5)and[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(N_(3))][PF_(6)](6).In addition,complexes 2,3 and 4 show distinct catalytic reactivity toward the disproportionation of hydrazine into *** results may be helpful to understand the vital role of the heterometal in some catalytic transformations promoted by heteromultinuclear complexes.

关键词： Metallic cooperativity heterobinuclear complex Hydrazine disproportionation Metallothiolate ligand Metal-sulfur cluster