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Dalton Trans. 2009 May 21;(19):3814-23. doi: 10.1039/b901508f. Epub 2009 Mar 24.

Highly selective hydroxylation of alkanes catalyzed by (micro-oxo)bis(micro-carboxylato)-bridged diiron(III) complexes: involvement of mononuclear iron(III) species in catalysis.

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School of Chemistry, Bharathidasan University, Tiruchirappalli, 620 024, India.


A few diiron(III) complexes [Fe2(O)(OAc)2(L1)2](ClO4)2, [Fe2(O)(OBz)2(L1)2](ClO4)2, [Fe2(O)(OAc)2(L2)2](ClO4)2 and [Fe2(O)(OBz)2(L2)2](ClO4)2, where L1=N,N-bis(pyrid-2-ylmethyl)-iso-butylamine, L2=N,N-bis(pyrid-2-ylmethyl)benzylamine, AcO=acetate and BzO=benzoate, have been isolated and characterized by means of elemental analysis and spectral and electrochemical methods. The molecular structures of the complexes and have been determined by single-crystal X-ray diffraction analysis and they possess a distorted bioctahedral geometry in which each iron atom is coordinated to the oxygen atom of the micro-oxo bridge, two oxygen atoms of the micro-benzoato bridges and three nitrogen atoms of L1 and L2 ligands capping the two ends of the diiron(III) cluster. The ESI-MS spectral data of the complexes reveal that the complexes remain intact in dichloromethane (DCM) solution. Upon adding one equivalent of Et3N to a mixture of one equivalent of the diiron(III) complexes and excess of m-chloroperbenzoic acid (m-CPBA) in DCM, an intense absorption band (lambdamax, 670-700 nm) appears, which corresponds to the species [Fe2(O)(OAc)(m-CPBA)(L)2]2+ (ESI-MS, m/z 466) suggested as the intermediate involved in the oxygenation reactions. All the present complexes show efficient alkane hydroxylation with 300-400 turn over numbers and good selectivities for cyclohexane (A/K, 10-14) and adamantane (3 degrees/2 degrees, 9-11). Interestingly, the formation of monoiron(III) species has been discerned in the alkane hydroxylation reactions beyond approximately 50 turnovers. The mononuclear 1:1 iron(III) complexes of L1 and L2 ligands generated in situ are also found to catalyze the oxygenation reactions with high selectivity and efficiency for cyclohexane (A/K, 10-14). Upon their reaction with m-CPBA in DCM, a characteristic absorption band (lambdamax, 600 nm, epsilonmax, 355 M(-1) cm(-1)) appears and decays at room temperature. This spectral feature is consistent with the mononuclear high-valent iron-oxo species suggested as an intermediate in the oxygenation reactions.

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