Reductive Binding of C‒O and Nitro Substrates at a Pyrazolate-Bridged Preorganized Dinickel Scaffold

by Thomas Kothe
Doctoral thesis
Date of Examination:2020-11-05
Date of issue:2020-12-15
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Marc Walter
Persistent Address: http://dx.doi.org/10.53846/goediss-8365

 

 

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Abstract

English

The transition-metal mediated conversion of C‒O multiple bond containing substrate plays an important role in various catalytic processes. Initially, this work investigates the alkylation of a pyrazolate-bridged preorganized dinickel scaffold with electrophilic methylation reagents and the subsequent insertion of CO into the resulting Ni‒C bond. This reaction pattern resembles the catalytic activity of the enzyme acetyl coA synthase. Furthermore, CO is also directly bound to the pyrazolate-bridged preorganized dinickel scaffold and subsequently reduced providing access to stable nickel formyl and nickel oxymethylene species. Additionally, the chemoselective reduction of aliphatic and aromatic nitro compound is described.
Keywords: nickel; reductive binding; transition metal complex; bimetallic complex; pyrazolate; nacnac; acetyl coa synthase; nickle hydride; CO reduction; nitro compounds
 
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