ISBN 9783843926676

978-3-8439-2667-6, Reihe Organische Chemie

Marta Ayerbe Garcia
New Developments in Late Transition Metal Complexes of Ferrocene Based Ligands and Study of Their Efficiency as Catalysts in Asymmetric Reactions

202 Seiten, Dissertation Universität Stuttgart (2016), Softcover, A5

Zusammenfassung / Abstract

This research aimed to develop novel types of ferrocene containing soft metal complexes and investigate their use in asymmetric catalysis. The study was motivated by the successful performance in asymmetric catalysis of the Pd(II) and Pt(II) based ferrocene metallacycle catalysts developed previously in our group.

Equivalent enantiopure ferrocenyl derivatives directly coordinated to Ni and Au had to our knowledge so far not yet been reported. Since on the one hand nickel represents a more cost-efficient option and on the other hand the very rich chemistry of homogenous gold catalysis has not yet been fully explored, the study of these two metals as metal centers of our systems was particularly attractive.

In this dissertation different strategies are described for nickelation attempts of ferrocenes. Driven by the nickelation attempts it was possible to generate a new type of sterically demanding P,N-pentaphenylferrocene ligands. These ligands were then coordinated with Pd and their catalytic activity was investigated in asymmetric allylic substitutions. Furthermore, unprecedented enantiopure ferrocenyl gold complexes (Au(I) and Au(II)) were successfully synthetized and characterizations by X-ray crystal structure analysis, electrochemical and computational methods were performed to better understand the surprisingly high tendency to adopt the rather unusual Au(II) oxidation state in a dinuclear diamagnetic system featuring a short Au(II)–Au(II) bond.