Small Molecule Activation of Copper and Iron Complexes with Bis(oxazoline) Ligands

Goswami, Vandana Esther

dc.contributor.advisor	Meyer, Franc Prof. Dr.
dc.contributor.author	Goswami, Vandana Esther
dc.date.accessioned	2017-09-22T08:05:16Z
dc.date.available	2017-09-22T08:05:16Z
dc.date.issued	2017-09-22
dc.identifier.uri	http://hdl.handle.net/11858/00-1735-0000-0023-3F0E-B
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-6498
dc.language.iso	eng	de
dc.publisher	Niedersächsische Staats- und Universitätsbibliothek Göttingen	de
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc	540	de
dc.title	Small Molecule Activation of Copper and Iron Complexes with Bis(oxazoline) Ligands	de
dc.type	doctoralThesis	de
dc.contributor.referee	Meyer, Franc Prof. Dr.
dc.date.examination	2016-10-17
dc.description.abstracteng	This work describes small molecule activation by copper and iron complexes with structurally and electronically modified bis(oxazoline) (BOX) ligand systems, focusing on dioxygen and nitric oxide as substrates. Dioxygen activation at low temperatures by copper(I) complexes with neutral BOX scaffolds generated the side on peroxo dicopper(II) systems that resemble the intermediates found in type III copper proteins, whereas those complexes with an anionic BOX-derived scaffold generated the bis(µ-oxido) dicopper(III) species. The bis(µ-oxido) system has recently been proposed as an active intermediate of pMMO. All complexes have been comprehensively characterized in solid state and solution, including single crystal X-ray crystallographic structure determination for representative examples, and the intermediates were screened for substrate reactivity. Moreover, triggered by protonation/deprotonation reactions, it was possible to interconvert the side-on peroxo dicopper(II) and bis(µ-oxido) dicopper(III) systems. The reaction of iron(II) BOX complexes with nitric oxide successfully generated a dinitrosyl iron complex that was isolated and characterized as well. In conclusion, BOX ligands that have been termed as a privileged ligand class in the field of asymmetric catalysis, have proved themselves to be useful in the field of bioinorganic chemistry as well.	de
dc.contributor.coReferee	Siewert, Inke Dr.
dc.subject.eng	small molecule activation	de
dc.subject.eng	type III copper proteins	de
dc.subject.eng	side-on peroxo dicopper(II)	de
dc.subject.eng	bis mu-oxido dicopper(III)	de
dc.subject.eng	nitric oxide	de
dc.subject.eng	dinitrosyl iron complex	de
dc.subject.eng	bis(oxazoline)	de
dc.identifier.urn	urn:nbn:de:gbv:7-11858/00-1735-0000-0023-3F0E-B-4
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.identifier.ppn	1004916434 100014769X

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