Tetra- and Decanuclear Iron(III) Phosphonates: Observance of a Rare P-C Bond Cleavage in a Homogeneous Medium - Centre de recherches Paul Pascal Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2009

Tetra- and Decanuclear Iron(III) Phosphonates: Observance of a Rare P-C Bond Cleavage in a Homogeneous Medium

Résumé

Reactions of tert-butylphosphonic acid (tBuPO3H2) with two different Fe(III) precursors have been investigated. The reaction of precursor complex [Fe3(μ3-O)(O2CPh)6(H2O)3]Cl with tBuPO3H2 in pyridine (py) leads to the formation of tetranuclear iron(III)phosphonate [Fe4O(tBuPO3)3(O2CPh)3(py)3Cl] * 3.5py (1) as single crystals. The change of the Fe(III) source to FeCl3 under similar reaction conditions results in the isolation of decanuclear complex [Fe10(OH)8(HPO4)(tBuPO3)8(tBuPO3H)4(py)8] * 4py * 5H2O (2). Compounds 1 and 2 have been characterized by elemental analysis, spectroscopic studies, and single-crystal X-ray diffraction studies. While the structure of 1 could be described as a tetrahedral cluster supported by benzoate and phosphonate ligands, the molecular structure of 2 is unprecedented in metal phosphonate chemistry. In the course of formation of 2, tBuPO3H2 undergoes a rare P-C bond cleavage at room temperature and produces the phosphate anion, which then acts as a template for the construction of a novel decanuclear iron-phosphate-phosphonate with a hitherto unknown core architecture. The temperature dependence of the T product in 2 reveals dominant antiferromagnetic interactions between Fe(III) centers.

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Matériaux
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Dates et versions

hal-00625391 , version 1 (21-09-2011)

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Ramaswamy Murugavel, Nayanmoni Gogoi, Rodolphe Clérac. Tetra- and Decanuclear Iron(III) Phosphonates: Observance of a Rare P-C Bond Cleavage in a Homogeneous Medium. Inorganic Chemistry, 2009, 48 (2), pp. 646-651. ⟨10.1021/ic8017562⟩. ⟨hal-00625391⟩

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