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The preparation, crystal structure and reactivity of a trimetallic Mn^III carboxylate cluster containing the dianion of methylsalicyloxime (Me-saoH₂), is reported. The reaction between Mn(OAc)₂·4H₂O and Me-saoH₂ in pyridine (py) produces the complex [Mn₃^IIIO(OAc)(Me-sao)₃(py)₄]·2py(1·2py) in very good yields. The neutral complex consists of a central triangular {Mn₃^IIIO} unit assembled together by three η¹:η¹:η¹:μ₂-oximato(−2) and one bridging AcO⁻ ligands. Oxidation of 1·2 py in MeCN in the presence of (NH₄)₂[Ce^IV(NO₃)₆] leads to the formation of complex [Mn₄^IVCe₂^IIIO₂(Me-sao)₆(NO₃)₄(OAc)₂(H₂O)₂]·6MeCN(2·6MeCN). Its centrosymmetric structure may be described as two {Mn₂^IVCe^IIIO}triangles linked through two η²:η²:η¹:μ₄ oximato(−2) ligands. Each {Mn₂^IVCe^IIIO} unit is held together via one η²:η¹:η¹:μ₃ and one η¹:η¹:η¹:μ₂-Me-sao²⁻ ligand, and one bridging acetate. Dc magnetic susceptibility …