Dinickel Complexes of the "Two-In-One" Pincer scaffold

von Pierre Goursot
Dissertation
Datum der mündl. Prüfung:2019-05-29
Erschienen:2019-11-11
Betreuer:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Inke Siewert
Zum Verlinken/Zitieren: http://dx.doi.org/10.53846/goediss-7715

 

 

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Bringing two metal ions in close proximity offers interesting perspectives for cooperative activation and catalytic transformation of substrates. Ditopic pyrazolate-based bridging ligands are known to represent valuable ligand scaffolds in this regard. These studies on bimetallic systems featuring metal-metal cooperativity (MMC) are often inspired by multimetallic sites found in the active centers of metalloenzymes. Metal-ligand cooperation (MLC) is a ubiquitous concept applied for the activation and transformation of organic substrates in catalysis. The (de)aromatization of organometallic systems exemplified by Milstein’s Ru catalyst, is a convenient method to perform polar bond dissociation during a catalytic event. The implementation of such a ligand motif in a bimetallic scaffold is an approach to combine both intramolecular MMC and MLC. The following work continued the investigation made by S. Samanta in 2015, in which a “Two-In-One” di-iron complex was synthesized. This work extended the development of similar organometallic complexes by exploring the chemistry of nickel. A major achievement of this work involves the introduction of a series of new dinickel complexes which were only different from each other by subtle structural modifications. Increased reactivities were observed by stepwise chemical modifications of the system. A highly reactive dinickel complex could be isolated. It displayed attractive reactivities toward the reversible cleavage of H2 by the possible cooperation of the ligand. This reactivity operated via a transverse intramolecular interaction, namely the dihydrogen bond. This subtype of hydrogen bond was stabilized by MMC. This work was an attempt to demonstrate the implication of both MMC and MLC during the chemical reaction of this new dinickel system.
Keywords: Dihydrogen Bond; Nickel hydride; Metal metal cooperation; Metal ligand cooperation; PNN ligand; Hydrogen bond; Hydrido Hydroxo; Pyrazolate; Dinickel
 
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