The use of methylsalicyloxime in manganese chemistry: A [Mn3III] triangle and its oxidation to a [Mn4IVCe2III] rod

The preparation, crystal structure and reactivity of a trimetallic MnIII 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 [Mn3IIIO(OAc)(Me-sao)3(py)4]·2py(1·2py) in very good yields. The neutral complex consists of a central triangular {Mn3IIIO} 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[CeIV(NO3)6] leads to the formation of complex [Mn4IVCe2IIIO2(Me-sao)6(NO3)4(OAc)2(H2O)2]·6MeCN(2·6MeCN). Its centrosymmetric structure may be described as two {Mn2IVCeIIIO}triangles linked through two η2:η2:η1:μ4 oximato(−2) ligands. Each {Mn2IVCeIIIO} 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 studies reveal the presence of dominant antiferromagnetic interactions in both complexes.

Graphical abstractThe preparation, crystal structure and reactivity of a trimetallic MnIII carboxylate cluster containing the dianion of 2-hydroxyethanone oxime (Me-saoH2), is reported. Oxidation of the trimetallic complex in the presence of (NH4)2[CeIV(NO3)6] leads to the formation of a [Mn4IVCe2III] species.Figure optionsDownload full-size imageDownload as PowerPoint slide