Tetradentate NHC/Thiolato and NHC/Alcoholato Hybrid Scaffolds – A Nickel(II) Complex as Bidentate Metalloligand in 3d Transition Metal Chemistry

by Giuseppe Lococciolo
Doctoral thesis
Date of Examination:2022-12-19
Date of issue:2023-03-08
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Inke Siewert
Referee:Dr. Carole Duboc
Referee:Dr. Matthias Otte
Referee:Dr. Lisa Vondung
Referee:Prof. Johannes Jun-Walker
Referee:Prof. Anna, Jun-Krawczuk
Persistent Address: http://dx.doi.org/10.53846/goediss-9763

 

 

Files in this item

Name:EMBARGO - Dissertation Giuseppe Lococciolo.pdf
Size:6.66Mb
Format:PDF
Description:PhD Dissertation (EMBARGO)

This file will be freely accessible after 2023-12-18.

Abstract

English

Research and development of N-heterocyclic carbene (NHC)-based ligands has flourished in recent decades. Herein, The new bis-imidazolinium proligands were designed and synthesized to serve as tetradentate bis(NHC)-dithiolato and bis(NHC)-dialcoholato ligands for the complexation of NiII. The proligands were designed to be capable of binding multiple metal cores in close proximity, and acting as a neutral metalloligand moiety for the complexation of 3d metals. The strong σ-donor and flexible π-acceptor character of the NHC and its redox-innocent nature are potentially beneficial to impart high stability and support metal-centered redox chemistry. A series of bimetallic and trimetallic complexes with 3d metals, such as FeII and CoII, was synthesized. Electrocatalytic hydrogen evolution was tested using trimetallic NiFeNi complex, and the results were discussed. Trimetallic NiCoNi complex showed an unprecedented zero-field SIM behaviour for a CoII complex with exclusive oxo-donors.
Keywords: Magnetism; NHC; Hydrogenase; Nickel Complexes; Single Molecular Magnets; Single Ion Magnets; Cobalt complexes; NHC-Alcoholato; zero-field SMM; electrocatalysis; NHC-thiolato; SQUID; Mößbauer