Preorganization within a pyrazolato-bridged bis-β-diketiminato dinickel frame as a key tool to access terminal sulfides and synergistically stabilized intermediates for acetyl-CoA synthase mimetic thioester formation

Tagliavini, Valeria

dc.contributor.advisor	Meyer, Franc Prof. Dr.
dc.contributor.author	Tagliavini, Valeria
dc.date.accessioned	2025-05-21T08:56:39Z
dc.date.available	2025-05-28T00:50:09Z
dc.date.issued	2025-05-21
dc.identifier.uri	http://resolver.sub.uni-goettingen.de/purl?ediss-11858/16009
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-11272
dc.format.extent	241	de
dc.language.iso	eng	de
dc.rights.uri	http://creativecommons.org/licenses/by/4.0/
dc.subject.ddc	540	de
dc.title	Preorganization within a pyrazolato-bridged bis-β-diketiminato dinickel frame as a key tool to access terminal sulfides and synergistically stabilized intermediates for acetyl-CoA synthase mimetic thioester formation	de
dc.type	doctoralThesis	de
dc.contributor.referee	Meyer, Franc Prof. Dr.
dc.date.examination	2024-07-22	de
dc.description.abstracteng	Bimetallic complexes are frequently employed in natural enzymes and in applications such as imaging, targeting, and catalysis, in order to exploit the synergy between two metal centers or to combine different functionalities. Herein, a dinickel complex supported by a pyrazolate-bridged bis-β-diketiminate ligand framework was employed to enable metal cooperativity and stabilize reactive intermediates. In particular, this complex was shown to accommodate a unique sulfido radical moiety, whose spectroscopic signatures have been elucidated. Stepwise transformations following sulfur activation allowed the construction of a thermodynamic square scheme, providing the S–H bond dissociation free energy of the corresponding hydrosulfido congener. Moreover, this bimetallic platform was shown to support an acetyl-CoA synthase mimetic cycle, in which a methyl complex stabilized by agostic interactions reacts with CO to yield a side-on acetyl complex. Upon reaction with thiols, a thioester was ultimately released. The intermediates and mechanism were investigated in detail. Finally, the scope of the ligand framework was extended to heterobimetallic [NiFe] and [NiMg] complexes.	de
dc.contributor.coReferee	Schneider, Sven Prof. Dr.
dc.contributor.thirdReferee	Alcarazo, Manuel Prof. Dr.
dc.subject.eng	nickel	de
dc.subject.eng	bimetallic complexes	de
dc.subject.eng	nacnac	de
dc.subject.eng	small molecule activation	de
dc.subject.eng	sulfido radical	de
dc.subject.eng	acetyl-CoA synthase	de
dc.subject.eng	agostic interacions	de
dc.subject.eng	PCET	de
dc.subject.eng	heterobimetallic complexes	de
dc.identifier.urn	urn:nbn:de:gbv:7-ediss-16009-1
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.description.embargoed	2025-05-28	de
dc.identifier.ppn	1926380355
dc.notes.confirmationsent	Confirmation sent 2025-05-21T09:45:02	de

Files in this item

Name:Dissertation_Valeria_Tagliavini.pdf

Size:44.51Mb

Format:PDF

View/Open

Name:: Dissertation_Valeria_Tagliavini.pdf
Size:: 44.51Mb
Format:: PDF

View/Open

This item appears in the following Collection(s)

Fakultät für Chemie (inkl. GAUSS) [743]

Show simple item record