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

Visvaganesan, Kusalendiran ; Suresh, Eringathodi ; Palaniandavar, Mallayan (2009) Highly selective hydroxylation of alkanes catalyzed by (μ -oxo)bis(μ -carboxylato)-bridged diiron(III) complexes: involvement of mononuclear iron(III) species in catalysis Dalton Transactions (19). pp. 3814-3823. ISSN 1477-9226

Full text not available from this repository.

Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/2009...

Related URL: http://dx.doi.org/10.1039/B901508F

Abstract

A few diiron(III) complexes [Fe2(O)(OAc)2(L1)2](ClO4)21, [Fe2(O)(OBz)2(L1)2](ClO4)22, [Fe2(O)(OAc)2(L2)2](ClO4)23 and [Fe2(O)(OBz)2(L2)2](ClO4)24, 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 2 and 4 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 μ-oxo bridge, two oxygen atoms of the μ-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 (λ max, 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° /2° , 9-11). Interestingly, the formation of monoiron(III) species has been discerned in the alkane hydroxylation reactions beyond ~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 ( λmax, 600 nm, ε max, 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.

Item Type:Article
Source:Copyright of this article belongs to Royal Society of Chemistry.
ID Code:30969
Deposited On:27 Dec 2010 06:54
Last Modified:05 Mar 2011 04:51

Repository Staff Only: item control page