Faculté des sciences

Synthesis, crystal structures and magnetic properties of trinuclear oxo-centered homo- and mixed-valence manganese pivalate complexes with imidazole (Im) and 1-methylimidazole (1-MeIm): [Mn3III0(02CCMe3)6 (Im)3](Me3CC02)•0.5Me3CC02H and [Mn2IIIMnII0(02CCMe3)6(1-MeIm)3]

Baca, Svetlana G. ; Stoeckli-Evans, Helen ; Ambrus, Christina ; Malinovskii, Stanislav T. ; Malaestean, Iurii ; Gerbeleu, Nicolae ; Decurtins, Silvio

In: Polyhedron, 2006, vol. 25, no. 18, p. 3617-3627

Two new μ3-oxo-centered trinuclear manganese complexes, one of them a homo-valence [Mn3III0(02CCMe3)6 (Im)3](Me3CC02)•0.5Me3CC02H (1) pivalate complex and the other a mixed-valence... Plus

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    Summary
    Two new μ3-oxo-centered trinuclear manganese complexes, one of them a homo-valence [Mn3III0(02CCMe3)6 (Im)3](Me3CC02)•0.5Me3CC02H (1) pivalate complex and the other a mixed-valence [Mn2IIIMnII0(02CCMe3)6(1-MeIm)3] (2) pivalate complex (where Im = imidazole, 1-MeIm = 1-methylimidazole), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, X-ray crystallography and magnetochemistry. Complexes 1 and 2 are μ3-oxo-trinuclear compounds with the three manganese atoms bridged by six pivalate groups. At each axial position there is an Im (1) or 1-MeIm (2) molecule. In both compounds, the manganese coordination geometry is slightly distorted octahedral, consisting of the oxygen of the central triangle, four oxygen atoms from bridging pivalate ligands, and a terminal Im or 1-MeIm nitrogen atom. The crystal packing of 1 involves hydrogen bonding between complex cations [Mn3O(Piv)6(Im)3]+ and outersphere pivalate ions, whereas in compound 2 interactions of the C–Hπ type, formed by both the aromatic and methyl C–H groups of 1-MeIm molecules, are present. Magnetic studies reveal that both compounds represent antiferromagnetically coupled, spin-frustrated triangular systems exhibiting weak to moderate exchange coupling constants.