期刊
DALTON TRANSACTIONS
卷 40, 期 32, 页码 8092-8107出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt01598a
关键词
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资金
- Council of Scientific and Industrial Research, New Delhi
- Department of Science and Technology (DST), New Delhi [SR/S1/IC-45/2003, SR/S5/BC-05/2006]
- DST, New Delhi [SR/S1/RFIC-01/2010]
- Indo-French Centre (IFCPAR) [IFC/A/4109-1/2009/993]
A series of mononuclear iron(III) complexes of the type [Fe(L)Cl-3], where L is a systematically modified N2O or N3O ligand with a methoxyethyl/tetrahydrofuryl ether oxygen donor atom, have been isolated and studied as models for catechol dioxygenases. The X-ray crystal structures of [Fe(L2)Cl-3](2), [Fe(L6)Cl-3] 6, [Fe(L5)(TCC)Cl] 5a, where H2TCC = tetrachlorocatechol, [Fe(L6)(TCC)Br] 6a, and the mu-oxo dimer [{Fe(L6)Cl}(2)O](ClO4)(2) 6b have been successfully determined. In [Fe(L2)Cl-3] 2 the N2O ligand is facially coordinated to iron(III) through the pyridine and secondary amine nitrogen atoms and the tetrahydrofuryl oxygen atom. In [Fe(L6)Cl-3] 6, [Fe(L5)(TCC)Cl] 5a and [Fe(L6)(TCC)Br] 6a the N3O donor ligands L5 and L6 act as a tridentate N3 donor ligand coordinated through two pyridine and one secondary amine nitrogen atoms, whereas the ether oxygen is not coordinated. The spectral and electrochemical properties of the adducts [Fe(L)(DBC)Cl] of 1-8, where H2DBC = 3,5-di-tert-butylcatechol, in DMF and their solvated adduct species [Fe(L)(DBC)(Sol)](+), where Sol = DMF/H2O, generated in situ in dichloromethane, respectively, have been investigated. The product analysis demonstrates that the adducts [Fe(L)(DBC) Cl] effect cleavage of catechol in the presence of O-2 in DMF to give mainly the intradiol (I) product with a small amount of the extradiol (E) product (E/I, 0.2: 1-0.7: 1). Interestingly, the solvated species [Fe(L)(DBC)(Sol)]+ derived from 1-4 cleave H2DBC to provide mainly the extradiol cleavage products with lower amounts of intradiol products (E/I, 2.3:1-4.3:1) in dichloromethane. In contrast, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 5-8 cleave H2DBC to provide both extradiol and intradiol products (E/I, 0.6:1-2.3:1) due to the involvement of the ether oxygen donor of the methoxyethyl/tetrahydrofuryl arm in the coordination to iron(III) upon removal of a chloride ion.
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