On the Catalytic Efficacy of Low-Oxidation State Group 14 Complexes

This outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metalmetal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.

Nominated as an outstanding Ph.D thesis by Monash University, Australia Provides details of a systematic investigation of the efficacy of group 14 complexes in catalysis Describes the first examples of well-defined group 14 complexes used in catalysis, with in-depth kinetic and computational studies outlining specific reaction pathways Offers a comprehensive discussion of low-oxidation-state group 14 chemistry, typically in the context of linking coordination state and ligand class to observed reactivity Includes supplementary material: sn.pub/extras

Autorentext
Terrance completed his undergraduate degree (MChem (Hons)) at the University of Bath, England, in May 2011. His Masters project was carried out under the supervision of Prof. Micheal Hill, where his interest in the development of earth-abundant element complexes as catalyts was born. During his PhD studies with Prof. Cameron Jones at Monash University, Australia, Terrance briefly worked with Prof. Simon Aldridge, University of Oxford, as a visiting student. After completing his PhD in August 2015, he moved to work with Prof. Matthias Driess, TU Belin, as a postdoctoral Fellow of the UniCat Cluster of Excellence.

Inhalt
General Introduction.- The Development of Extremely Bulky Amide Ligands and their Application to the Synthesis of Group 14 Element(II) Halides.- Synthesis and Reactivity of Heavier Alkyne Analogues Stabilised by Extremely Bulky Amide Ligands.- Reactivity of Low-Coordinate Group 14 Element(II) Hydride Complexes.- Stoichiometric Reactivity and Catalytic Applications of Heavier Tetrelene Derivatives.- The Use of a Bulky Boryl-Substituted Amide Ligand in Low-Oxidation State Group 14 Element Chemistry.