A series of 3d metal complexes prepared by in situ reactions of a flexible diacylhydrazine ligand: synthesis,structures and magnetic properties |
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| Authors: | Kai Wang Zi-Lu Chen Hua-Hong Zou Yan Li Fu-Pei Liang |
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| Affiliation: | 1.Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering,Guilin University of Technology,Guilin,China;2.State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmacy,Guangxi Normal University,Guilin,China |
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| Abstract: | The coordination reactions of 3d metal salts with malonic acid N,N′-bis(salicyloyl) bishydrazide (H6mbshz) afforded three complexes, namely [Cu2(H2bshz)(Py)4Cl2]·Py (1) (Py = pyridine), [Fe2(bshz)(Py)2] (2) and the known complex [Ni4(aehba)2(DMF)2(H2O)2]·2DMF (3), where bshz = N,N′-bis(salicyloyl)hydrazine anion and aehba4? = azo-enolic-2-hydroxybenzamide anion. The X-ray crystal structures of all three complexes have been obtained. Complexes 1 and 2 are composed of N–N-bridged binuclear units, while complex 3 displays a planar tetranuclear structure in which four Ni(II) centers are linked together by N–N and N=N bonds. The bshz anions in 1 and 2 and aehba4? anions in 3 were all generated in situ from H6mbshz. A mechanism for these reactions is proposed, involving tandem C–N cleavage and C–N/N–N coupling processes via free radical intermediates. Magnetic investigations revealed dominant antiferromagnetic interactions between the metallic centers of each complex. |
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