title: A new tripodal iron(III) monophenolate complex: effects of ligand basicity, steric hindrance, and solvent on regioselective extradiol cleavage.
abstract: The new iron(III) complex [Fe(L3)Cl(2)], where H(L3) is the tripodal monophenolate ligand N,N-dimethyl-N'-(pyrid-2-ylmethyl)-N'-(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine, has been isolated and studied as a structural and functional model for catechol dioxygenase enzymes. The complex possesses a distorted octahedral iron(III) coordination geometry constituted by the phenolate oxygen, pyridine nitrogen and two amine nitrogens of the tetradentate ligand, and two cis-coordinated chloride ions. The Fe-O-C bond angle (134.0 degrees) and Fe-O bond length (1.889 Angstrom) are very close to those (Fe-O-C, 133 degrees and 148 degrees, Fe-O(tyrosinate), 1.81 and 1.91 Angstrom) of protocatechuate 3,4-dioxygenase enzymes. When the complex is treated with AgNO(3), the ligand-to-metal charge transfer (LMCT) band around 650 nm (epsilon, 2390 M(-1) cm(-1)) is red shifted to 665 nm with an increase in absorptivity (epsilon, 2630 M(-1) cm(-1)) and the Fe(III)/Fe(II) redox couple is shifted to a slightly more positive potential (-0.329 to -0.276 V), suggesting an increase in the Lewis acidity of the iron(III) center upon the removal of coordinated chloride ions. Furthermore, when 3,5-di-tert-butylcatechol (H(2)DBC) pretreated with 2 mol of Et(3)N is added to the complex [Fe(L3)Cl(2)] treated with 2 equiv of AgNO(3), two intense catecholate-to-iron(III) LMCT bands (719 nm, epsilon, 3150 M(-1) cm(-1); 494 nm, epsilon, 3510 M(-1) cm(-1)) are observed. Similar observations are made when H(2)DBC pretreated with 2 mol of piperidine is added to [Fe(L3)Cl(2)], suggesting the formation of [Fe(L3)(DBC)] with bidentate coordination of DBC(2-). On the other hand, when H(2)DBC pretreated with 2 mol of Et(3)N is added to [Fe(L3)Cl(2)], only one catecholate-to-iron(III) LMCT band (617 nm; epsilon, 4380 M(-1) cm(-1)) is observed, revealing the formation of [Fe(L3)(HDBC)(Cl)] involving monodentate coordination of the catecholate. The appearance of the DBSQ/H(2)DBC couple for [Fe(L3)(DBC)] at a potential (-0.083 V) more positive than that (-0.125 V) for [Fe(L3)(HDBC)(Cl)] reveals that chelated DBC(2-) in the former is stabilized toward oxidation more than the coordinated HDBC(-). It is remarkable that the complex [Fe(L3)(HDBC)(Cl)] undergoes slow selective extradiol cleavage (17.3%) of H(2)DBC in the presence of O(2), unlike the iron(III)-phenolate complexes known to yield only intradiol products. It is probable that the weakly coordinated (2.310 Angstrom) -NMe(2) group rather than chloride in the substrate-bound complex is displaced, facilitating O(2) attack on the iron(III) center and, hence, the extradiol cleavage. In contrast, when the cleavage reaction was performed in the presence of a stronger base-like piperidine before and after the removal of the coordinated chloride ions, a faster intradiol cleavage was favored over extradiol cleavage, suggesting the importance of the bidentate coordination of the catecholate substrate in facilitating intradiol cleavage. Also, intradiol cleavage is favored in dimethylformamide and acetonitrile solvents, with enhanced intradiol cleavage yields of 94 and 40%, respectively.
authors.affiliation: School of Chemistry, Bharathidasan University, Tiruchirapalli 620 024, India.
authors.forename: Ramasamy
authors.initials: R
authors.lastname: Mayilmurugan
authors.forename: Eringathodi
authors.initials: E
authors.lastname: Suresh
authors.forename: Mallayan
authors.initials: M
authors.lastname: Palaniandavar