2006 Volume 79 Issue 2 Pages 252-261
The peroxodiiron(III) complexes [Fe2(O)(O2)(OAc)(hexpy)](CF3SO3) (2) and [Fe2(O)(O2)(OAc)(tripy)2](ClO4) (4) (hexpy = 1,2-di[6-bis(2-pyridyl)methyl-2-pyridyl]ethane and tripy = 2-di(2-pyridyl)methyl-6-methylpyridine) were prepared by addition of H2O2 to the di(μ-acetato)-μ-oxodiiron(III) complexes [Fe2(O)(OAc)2(hexpy)](CF3SO3)2 (1c) and [Fe2(O)(OAc)2(tripy)2](ClO4)2 (3) in MeCN, respectively. The peroxo complex 2 was isolated as a purple solid, but 4 could not be due to its instability. Detailed spectral studies of 2 and 4 revealed the unique triply bridged μ-acetato-μ-oxo-μ-1,2-peroxodiiron(III) core structures. The spontaneous decomposition of 2 and 4 in various solvent systems was kinetically investigated. The half-life of 2 and 4 in dry MeCN was 8.7 h at 300 K and 10 min at 263 K, respectively, clearly showing that the thermal stability of 2 is markedly enhanced by the hexpy ligand.
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