title: Biomimetic iron(III) complexes of N3O and N3O2 donor ligands: protonation of coordinated ethanolate donor enhances dioxygenase activity.
abstract: A series of iron(III) complexes 1-4 of the tripodal tetradentate ligands N,N-bis(pyrid-2-ylmethyl)-N-(2-hydroxyethyl)amine H(L1), N,N-bis(pyrid-2-ylmethyl)-N-(2-hydroxy- propyl)amine H(L2), N,N-bis(pyrid-2-ylmethyl)-N-ethoxyethanolamine H(L3), and N-((pyrid-2-ylmethyl)(1-methylimidazol-2-ylmethyl))-N-(2-hydroxyethyl)amine H(L4), have been isolated, characterized and studied as functional models for intradiol-cleaving catechol dioxygenases. In the X-ray crystal structure of [Fe(L1)Cl(2)] 1, the tertiary amine nitrogen and two pyridine nitrogen atoms of H(L1) are coordinated meridionally to iron(III) and the deprotonated ethanolate oxygen is coordinated axially. In contrast, [Fe(HL3)Cl(3)] 3 contains the tertiary amine nitrogen and two pyridine nitrogen atoms coordinated facially to iron(III) with the ligand ethoxyethanol moiety remaining uncoordinated. The X-ray structure of the bis(μ-alkoxo) dimer [{Fe(L5)Cl}(2)](ClO(4))(2)5, where HL is the tetradentate N(3)O donor ligand N,N-bis(1-methylimidazol-2-ylmethyl)-N-(2-hydroxyethyl)amine H(L5), contains the ethanolate oxygen donors coordinated to iron(III). Interestingly, the [Fe(HL)(DBC)](+) and [Fe(HL3)(HDBC)X] adducts, generated by adding ∼1 equivalent of piperidine to solutions containing equimolar quantities of iron(III) complexes 1-5 and H(2)DBC (3,5-di-tert-butylcatechol), display two DBC(2-)→ iron(III) LMCT bands (λ(max): 1, 577, 905; 2, 575,915; 3, 586, 920; 4, 563, 870; 5, 557, 856 nm; Δλ(max), 299-340 nm); however, the bands are blue-shifted (λ(max): 1, 443, 700; 2, 425, 702; 3, 424, 684; 4, 431, 687; 5, 434, 685 nm; Δλ(max), 251-277 nm) on adding 1 more equivalent of piperidine to form the adducts [Fe(L)(DBC)] and [Fe(HL3)(HDBC)X]. Electronic spectral and pH-metric titration studies in methanol disclose that the ligand in [Fe(HL)(DBC)](+) is protonated. The [Fe(L)(DBC)] adducts of iron(III) complexes of bis(pyridyl)-based ligands (1,2) afford higher amounts of intradiol-cleavage products, whereas those of mono/bis(imidazole)-based ligands (4,5) yield mainly the auto-oxidation product benzoquinone. It is remarkable that the adducts [Fe(HL)(DBC)](+)/[Fe(HL3)(DBC)X] exhibit higher rates of oxygenation affording larger amounts of intradiol-cleavage products and lower amounts of benzoquinone.
authors.affiliation: Centre for Bioinorganic Chemistry, School of Chemistry, Bharathidasan University, Tiruchirappalli, 620 024, India.
authors.forename: Karuppasamy
authors.initials: K
authors.lastname: Sundaravel
authors.forename: Muniyandi
authors.initials: M
authors.lastname: Sankaralingam
authors.forename: Eringathodi
authors.initials: E
authors.lastname: Suresh
authors.forename: Mallayan
authors.initials: M
authors.lastname: Palaniandavar
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002396:Catechols / Q000378:metabolism; D049308:Dioxygenases / Q000737:chemistry / Q000378:metabolism*; D004563:Electrochemistry; D004583:Electrons; D000431:Ethanol / Q000737:chemistry*; D006018:Glycols / Q000378:metabolism; D006863:Hydrogen-Ion Concentration; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D011522:Protons
chemical_list: D002396:Catechols; D006018:Glycols; D008024:Ligands; D009942:Organometallic Compounds; D011522:Protons; D000431:Ethanol; D007501:Iron; D049308:Dioxygenases; C034221:catechol; D010100:Oxygen