Reaction behavior of iron and copper complexes towards dioxygen

To provide a better understanding of the reactions of iron and copper proteins with dioxygen, the corresponding reactions of small molecule model complexes with dioxygen were analysed using spectroscopic and kinetic methods. Special attention focused upon the binding and activation of dioxygen by iron proteins such as hemerythrin (Hr) and protocatechuat-3,4-dioxygenase (3,4-PCD) and by copper proteins like hemocyanin (Hc) and tyrosinase. Iron complexes of the ligand tmpa (tmpa = tris[(2-pyridyl)methyl]amine, also known as tpa in literature) were synthesised and modifications of the tmpa ligand were made. Increasing as well as decreasing chelate ring sizes in the highly active complex [Fe(tmpa)(dbc)]B(C6H5)4 (dbc = 3,5-di-tert-butylcatecholate dianion), only resulted in decreased reactivity of the investigated compounds. A detailed low-temperature stopped-flow investigation of the reaction of dioxygen with [Fe(tmpa)(dbc)]B(C6H5)4 was performed and activation parameters of Delta H# = 23 +- 1 kJ mol-1 and Delta S# = -199 +- 4 J mol-1 K-1 were obtained. Crystal structures of bromo-(tetrachlorocatecholato-O,O\u27)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27)-iron(III) (2), (mu-oxo)-bis(bromo)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27,N\u27\u27\u27)-diiron(III) (3), dichloro-((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-iron(III) (4) and (tetrabromocatecholato-O,O\u27)((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-iron(III) (5) are reported (Chapter 2). Besides altering the chelate ring size the influence of the donor atoms of the ligand on catechol dioxygenase reactivity was investigated. Two derivatives of the tmpa ligand (uns-penp and acetyl-uns-penp) were synthesised, where one aromatic nitrogen donor was replaced by an aliphatic nitrogen donor. The iron(III) complexes of the tripodal ligands N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamine (uns-penp), [Fe(uns-penp)Cl2]ClO4 x CH3CN, [{Fe(uns-penp)Cl}2O](ClO4)2 x 2CH3CN and the amide derivative N-Acetyl-N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamine (acetyl-uns-penp), [Fe2(acetyl-uns-penp)2O](ClO4)2 x H2O, [Fe(acetyl-uns-penp)(tcc)Br] x (C2H5)2O and [{Fe(acetyl-uns-penp)(tcc)}2O] x (C2H5)2O x CH3OH were synthesised and characterised. Catechol dioxygenase reactivity of in situ prepared complex solutions only showed slower reactions in comparison with the iron tmpa system (Chapter 3). Corresponding ligand system variations in the small molecule model complexes of copper proteins were made and analysed with respect to dioxygen reactivity. Intramolecular ligand hydroxylation was observed during the reactions of dioxygen with the dicopper(I) complexes of the ligands L3 (L3 = alpha,alpha\u27-bis[(2-pyridylethyl)amino]-m-xylene) and L5 (L5 = alpha,alpha\u27-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)-amino]-m-xylene). The dinuclear copper(I) complex [Cu2L5](ClO4)2 and the dicopper(II) complex [Cu2(L3-O)(OH)(ClO4)]ClO4 were characterised by single-crystal X-ray structure analysis. Furthermore, phenolate-bridged complexes were synthesised with the ligand L4-OH and Me-L5-OH (structurally characterised: [Cu2(L4-O)Cl3] with L4 = alpha,alpha\u27-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylene and [Cu2(Me-L5-O)(mu-X)](ClO4)2 x nH2O with Me-L5-OH = 2,6-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-4-methylphenol and X = C3H3N2- (prz), MeCO2- and N3-). Temperature-dependent magnetic studies revealed the antiferromagnetic coupling of the copper ions of these complexes (Chapter 4). The reactions of dioxygen with copper(I) complexes of the tridentate ligands 1,1,4,7,7-pentamethyldiethylethylenetriamine (Me5dien), 1,1,4,7,7-pentaethyldiethylethylenetriamine (Et5dien), N-methyl-[bis(2-pyridyl)methyl]amine (Me-bpa) and N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amine (MeL) have been investigated using low-temperature stopped-flow techniques. The formation of a bis(mu-oxo) copper complex as a reactive intermediate could only be detected spectroscopically at low temperatures for [Cu(Me5dien)(CH3CN)]ClO4 and allowed a quantitative kinetic analysis to be performed. Crystal structures of the copper(II) complexes [(Me-bpa)Cu(Cl)2], [{(Me-bpa)Cu(Cl)(ClO4)}2], [{(MeL)Cu(Cl)(ClO4)}2] and [(MeL)Cu(NCS)2] are reported. (Chapter 5)Zum besseren Verständnis der Reaktionen von Eisen- und Kupferproteinen mit elementarem Sauerstoff wurden im Rahmen dieser Arbeit für Eisen- und Kupferproteine Modellkomplexe mit geringer Molekularmasse mit spektroskopischen oder kinetischen Methoden untersucht. Besondere Aufmerksamkeit wurde hierbei der Bindung und der Aktivierung von elementarem Sauerstoff durch die Eisenproteine, wie z. B. Hämerythrin (Hr) und Protocatechuat-3,4-dioxygenase (3,4-PCD), und die Kupferproteine, wie z. B. Hämocyanin (Hc) und Tyrosinase, gewidmet. Bezüglich der Modelle für Eisenenzyme wurde der Ligand tmpa (tmpa = tris[(2-pyridyl)methyl]amin; in der Literatur auch mit tpa abgekürzt) untersucht und systematisch variiert. Die Vergrößerung und Verkleinerung der Chelatringgröße im hochreaktiven Komplex [Fe(tmpa)(dbc)]B(C6H5)4 (dbc = 3,5-Di-tert-butylcatecholat Dianion) führte nur zu einer verringerten Reaktivität der untersuchten Verbindungen. Die Reaktion von elementaren Sauerstoff mit [Fe(tmpa)(dbc)]B(C6H5)4 wurde mittels der Tieftemperatur-\u27stopped-flow\u27-Technik untersucht und ergab die Aktivierungsparameter Delta H# = 23 +- 1 kJ mol-1 und Delta S# = -199 +- 4 J mol-1 K-1. Weiterhin wurden die Kristallstrukturanalysen der Verbindungen bromo-(tetra-chlorocatecholato-O,O\u27)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27)-eisen(III) (2), (mü-oxo)-bis(bromo)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27,N\u27\u27\u27)-dieisen (III) (3), dichloro-((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-eisen (III) (4) und (tetrabromocatecholato-O,O\u27)((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl) amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-eisen (III) (5) beschrieben (Kapitel 2). Neben der Änderung der Chelatringgröße wurde auch der Einfluss der Donoratome des Liganden untersucht. Dazu wurden abgeleitet vom tmpa zwei Liganden (uns-penp und acteyl-uns-penp) synthetisiert, bei denen ein aromatischer Stickstoff durch einen aliphatischen Stickstoff ersetzt wurde. Die Eisen(III)-Komplexe mit den tripodalen Liganden N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamin (uns-penp), [Fe(uns-penp)Cl2]ClO4 x CH3CN, [{Fe(uns-penp)Cl}2O](ClO4)2 x 2CH3CN und dem Amidderivat N-Acetyl-N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamin (acetyl-uns-penp), [Fe2(acetyl-uns-penp)2O](ClO4)2 x H2O, [Fe(acetyl-uns-penp)(tcc)Br] x (C2H5)2O und [{Fe(acetyl-uns-penp)(tcc)}2O] x (C2H5)2O x CH3OH wurden synthetisiert und charakterisiert. Untersuchungen zur Catecholdioxygenasereaktivität der in situ dargestellten Komplexlösungen zeigten nur langsamere Reaktionen im Vergleich zu dem Eisen-tmpa-System (Kapitel 3) Die Ligandensysteme für Modelle von Kupferproteinen wurden nach denselben Gesichtspunkten verändert wie bei den Modellen für die Eisenproteine. Intramolekulare Hydroxylierung des Liganden war bei der Reaktion von elementaren Sauerstoff mit Dikupfer(I)-Komplexen der Liganden L3 (L3 = alpha,alpha\u27-bis[(2-pyridylethyl)amino]-m-xylol) und L5 (L5 = alpha,alpha\u27-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)-amino]-m-xylol) zu beobachten. Der dinukleare Kupfer(I)-Komplex [Cu2L5](ClO4)2 und der Dikupfer(II)-Komplex [Cu2(L3-O)(OH)(ClO4)]ClO4 konnten durch Einkristallröntgenstrukturanalyse charakterisiert werden. Zusätzlich wurden Phenolatverbrückte Komplexe mit den Liganden L4-OH und Me-L5-OH synthetisiert (Strukturlösungen für [Cu2(L4-O)Cl3] mit L4 = alpha,alpha\u27-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylol und [Cu2(Me-L5-O)(mü-X)](ClO4)2 x nH2O (Me-L5-OH = 2,6-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-4-methylphenol und X = C3H3N2- (prz), MeCO2- und N3-). Temperaturabhängige magnetische Untersuchungen zeigten antiferromagnetische Kopplung der Kupferionen in diesen Komplexen (Kapitel 4). Die Reaktionen von elementaren Sauerstoff mit Kupfer(I)-Komplexen der dreizähnigen Liganden 1,1,4,7,7-pentamethyldiethylethylenetriamin (Me5dien), 1,1,4,7,7-pentaethyldiethylethylenetriamin (Et5dien), N-methyl-[bis(2-pyridyl) methyl]amin (Me-bpa) und N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amin (MeL) mit Hilfe der Tieftemperatur-\u27stopped-flow\u27-Technik untersucht. Die Bildung eines bis(mü-oxo)-Kupferkomplexes konnte dabei bei tiefen Temperaturen nur für den Komplex [Cu(Me5dien)(CH3CN)]ClO4 spektroskopisch beobachtet und quantitativ kinetisch analysiert werden. Die Komplexe [(Me-bpa)Cu(Cl)2], [{(Me-bpa)Cu(Cl)(ClO4)}2], [{(MeL)Cu(Cl)(ClO4)}2] und [(MeL)Cu(NCS)2] konnten kristallographisch charakterisiert werden. (Kapitel 5

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