Iron(III) complexes of tridentate 3N ligands as functional models for catechol dioxygenases: the role of ligand N-alkyl substitution and solvent on reaction rate and product selectivity

A series of iron(III) complexes of the type [Fe(L)Cl3], where L is the variously N-alkyl-substituted bis(pyrid-2-ylmethyl)amine ligand such as bis(pyrid-2-ylmethyl)amine (L1), N,N-bis(pyrid-2-ylmethyl)methylamine (L2), N,N-bis(pyrid-2-ylmethyl)-n-propylamine (L3), N,N-bis(pyrid-2-ylmethyl)-iso-butylamine (L4), N,N-bis(pyrid-2-ylmethyl)-iso-propylamine (L5), N,N-bis(pyrid-2-ylmethyl)cyclohexylamine (L6), and N,N-bis(pyrid-2-ylmethyl)-tert-butylamine (L7), have been isolated and characterized by elemental analysis and spectral and electrochemical methods. The crystal structures of the complexes [Fe(L2)Cl3] 2, [Fe(L3)Cl3] 3, and the complex-substrate adduct [Fe(L5)(TCC)(NO3)] 5a, where TCC2- is the tetrachlorocatecholate dianion, have been determined by single-crystal X-ray crystallography. The complexes [Fe(L2)Cl3] 2 and [Fe(L3)Cl3] 3 possess a distorted octahedral geometry, in which the linear tridentate 3N ligands are cis-facially coordinated to the iron(III) center, and three chloride ions occupy the remaining coordination sites. The replacement of the N-methyl group in 2 by N-n-propyl group as in 3 leads to the formation of the Fe-Npy bonds and also the Fe-Cl bonds located trans to them of different lengths. The catecholate adduct 5a also possesses a distorted octahedral geometry, in which the ligand is cis-facially coordinated to iron(III) center, TCC2- is asymmetrically chelated trans to the two pyridyl moieties of the ligand, and one of the oxygen atoms of the nitrate ion occupies the sixth coordination site. All of the present complexes have been interacted with simple and substituted catechols. The catecholate adducts [Fe(L)(DBC)Cl] and [Fe(L)(DBC)(Sol)]+, where H2DBC is 3,5-di-tert-butylcatechol and Sol = H2O/CH3CN, have been generated in situ, and their spectral and redox properties and dioxygenase activities have been studied in dimethylformamide and dichloromethane solutions. All of the complexes catalyze the cleavage of H2DBC using molecular oxygen to afford both intra- and extradiol cleavage products. The formation of extradiol cleavage products is facilitated by cis-facial coordination of the 3N ligands and availability of vacant coordination site on iron(III) center for dioxygen binding. It is remarkable that the nature of the N-alkyl substituent in 3N ligands controls the regioselectivity of cleavage, with the n-propyl, iso-butyl, iso-propyl, and cyclohexyl groups enhancing the yield of extradiol products (46-68%) in dichloromethane. The rate of oxygenation depends upon the solvent and the Lewis acidity of iron(III) center as modified by the sterically demanding N-alkyl groups-length and degree of substitution. The plot of log (kO2) versus energy of the low-energy DBC2--to-iron(III) LMCT band is linear, demonstrating the importance of the Lewis acidity of the iron(III) center in dictating the rate of the dioxygenase reaction