Synthesis, structure and properties of heterotrinuclear carboxylate complexes [Fe2M(Ca, Sr, Ba)O(CCl3COO)(6)(THF)n]

Three novel mu(3)-oxo trinuclear carboxylates [Fe2CaO(CCl3COO),(THF)(4)] center dot THF (1), [Fe2SrO(CCl3COO)(6)(THF)(6)] center dot 0.5H(2)O center dot 0.5THF (2) and [Fe2BaO(CCl3COO)(6)(THF)(6)] center dot 0.5H(2)O center dot 0.5THF (3) have been synthesised and subsequently characterised by X-ray structure analysis, thermal gravimetry (TG), infra red (IR) spectroscopy and magnetic measurements. Compounds I and 3 are molecular complexes with s- and d-metals displayed in the apexes of isosceles triangles with a triply bridging oxygen atom at its centre. The Ca center dot center dot center dot Fe and Ba center dot center dot center dot Fe separations have the values 3.750(1) and 4.177(1) angstrom, respectively. In comparison with these. Fe center dot center dot center dot Fe separations, 3.229(2) angstrom in 1 and 3.201(1) angstrom in 3, appear much shorter. The molecular complexes obey C-2 symmetry with the twofold axis passing through s metal and mu(3)-oxo atom. The coordination numbers are 6, 7 and 9 for iron. calcium and barium correspondingly. Magnetic studies reveal the presence of an antiferromagnetic exchange in the isosceles triangular skeletons of the trinuclear species. Using the spin Hamiltonian H = -2J(12)[S1S2], the fitting parameters g(Fe) = 2.00. J(Fe-Fe) = -58.90 cm(-1) for 1 and -60.40 cm(-1) for 3; g(Fe) = 2.14, J(Fe-Fe) = -75.40 cm(-1) for 2 have been estimated.