Binding of ligands containing carbonyl and phenol groups to iron(iii): new Fe6, Fe10 and Fe12 coordination clusters

Abstract

The initial use of ligands 2′-hydroxyacetophenone (HL¹), 2-hydroxybenzophenone (HL²) and 2,2′-dihydroxybenzophenone (H₂L³) in iron(III) chemistry is described. The syntheses and crystal structures are reported for five iron(III) clusters: [Fe₁₀O₄(OMe)₁₄(L¹)₆(MeOH)₂](NO₃)₂·3MeOH (1·3MeOH), [Fe₁₂O₄(OH)(OMe)₁₇(L¹)₈](ClO₄)₂·2H₂O (2·2H₂O), [Fe₁₀O₄(OMe)₁₄Cl₄(L²)₄(MeOH)₂] (3), [Fe₁₀O₄(OMe)₁₄(L²)₆(py)₂](ClO₄)₂·MeOH (4·MeOH), where py = pyridine, and [Fe₆O₂(OEt)₆(O₂CMe)₂(L³)₂(HL³)₂] (5). The molecular structures of the decanuclear clusters 1, 3 and 4 are organized around a {Fe₁₀(μ₄-O)₄(μ₃-OMe)₂(μ-OMe)₁₂}⁸⁺ core consisting of ten {Fe₃O₄} face-sharing defective cubane units. The core of 2 consists of a {Fe₁₂(μ₄-O)₄(μ₃-OMe)₄(μ-OH)(μ-OMe)₁₃}¹⁰⁺ unit composed of twelve {Fe₃O₄} face-sharing defective cubanes. The ligands (L¹)⁻ and (L²)⁻ in 1–4 adopt the O,O′-bidentate chelating coordination mode and their roles are to terminate the further aggregation of the Fe^III/O²⁻/RO⁻ cores. Complex 5 contains the {Fe₆(μ₄-O)₂(μ-OEt)₆(μ-O_carbonyl)₂}⁴⁺ core, where the μ-O_carbonyl atoms are the bridging carbonyl oxygens of the two η¹:η²:η¹:μ (L³)²⁻ ligands; the (HL³)⁻ groups behave as O_phenolate, O_carbonyl-bidentate chelating ligands with the neutral hydroxyl group being unbound to the Fe^III atoms. The core is composed of four {Fe₃O₄} face-sharing defective cubanes. The Fe^III atoms in 1–5 are all six-coordinate with distorted octahedral geometries. The IR spectra of the complexes are discussed in terms of the known coordination modes of the ligands and the ionic character of nitrates and perchlorates. Variable-temperature magnetic susceptibility and variable-field magnetization measurements establish that 2, 3 and 5 have S = 3, 0 and 5 ground states, respectively. The susceptibility data for 5 were fitted using a 3-J model indicating the simultaneous presence of both antiferromagnetic and ferromagnetic Fe^III⋯Fe^III exchange interactions. Known magnetostructural correlations in oxido-bridged iron(III) systems have been applied to rationalise the magnetic behaviour of the three clusters. The results of the present study demonstrate the utility of HL¹, HL² and H₂L³ in the stabilisation of robust iron(III)/oxido/alkoxido clusters.