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

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Springer, Feb 14, 2017 - Science - 243 pages
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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 metal–metal 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.

 

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Contents

1 General Introduction
1
2 The Development of Extremely Bulky Amide Ligands and Their Application to the Synthesis of Group 14 ElementII Halide Complexes
13
3 Synthesis and Reactivity of Heavier Alkyne Analogues Stabilised by Extremely Bulky Amide Ligands
43
4 Reactivity of LowCoordinate Group 14 ElementII Hydride Complexes
113
5 Stoichiometric Reactivity and Catalytic Applications of Heavier Tetrylene Derivatives
146
6 The Use of a Bulky BorylSubstituted Amide Ligand in LowOxidation State Group 14 Element Chemistry
205
General Synthetic Considerations
238
Appendix B Crystallographic Data
239
Computational Studies
240
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About the author (2017)

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.

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