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

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Title Tetra- and Decanuclear Iron(III) Phosphonates: Observance of a Rare P-C Bond Cleavage in a Homogeneous Medium
 
Creator MURUGAVEL, R
GOGOI, N
CLERAC, R
 
Subject single-molecule magnets
tert-butyl phosphate
structural diversity
metal-phosphonate
complexes
ligands
clusters
transformations
tetranuclear
precursors
 
Description Reactions of tent butylphosphonic acid ((t)BuPO(3)H(2)) with two different Fe(III) precursors have been investigated. The reaction of precursor complex [Fe(3)(mu(3)-O)(O(2)CPh)(6)(H(2)O)(3)]Cl with (t)BuPO(3)H(2) in pyridine (py) leads to the formation of tetranuclear iron(III)phosphonate [Fe(4)O((t)BuPO(3))(3)(O(2)CPh)(3)(py)(3)Cl]center dot 3.5py (1) as single crystals. The change of the Fe(III) source to FeCl(3) under similar reaction conditions results in the isolation of decanuclear complex [Fe(10)(OH)(8)(HPO(4))((t)BUPO(3))(8)((t)BuPO(3)H)(4)(py)center dot 4py center dot 5H(2)O (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, (t)BuPO(3)H(2) 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 chi(T) product in 2 reveals dominant antiferromagnetic interactions between Fe(III) centers.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-15T01:32:15Z
2011-12-26T12:49:10Z
2011-12-27T05:34:56Z
2011-07-15T01:32:15Z
2011-12-26T12:49:10Z
2011-12-27T05:34:56Z
2009
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 48(2), 646-651
0020-1669
http://dx.doi.org/10.1021/ic8017562
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4117
http://hdl.handle.net/10054/4117
 
Language en