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

Terrance John Hadlington

• Publisher: Springer
• Year: 2017
• Print ISBN:
  9783319518060
• eBook ISBN:
  9783319518077
• Topic: Physical Sciences
• Subtopic: Inorganic Chemistry

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.

Table of contents

• Supervisor’s Foreword
• Preface
• Parts of this thesis have been published in the following journal articlesEfficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido-Germanium(II) and Tin(II) Hydride Complexes; Hadlington, T. J., Hermann, M., Frenking, G., and Jones, C., accepted to ACS Catalysis.Stabilization of a Two-Coordinate, Acyclic Diaminosilylene (ADASi): Completion of the Series of Isolable Diaminotetrylenes, :E(NR2)2 (E = Group 14 Element); Hadlington, T. J., Abdalla, J. A. B., Tirfoin, R., Aldridge, S., and Jones., C., Chem. Commun., 2016, 52, 1717–1720.Two-Coordinate Group 14 Element(II) Hydrides as Reagents for the Facile, and Sometimes Reversible, Hydrogermylation/Hydrostannylation of Unactivated Alkenes and Alkynes; Hadlington, T. J., Hermann, M., Frenking, G., and Jones, C., Chem. Sci., 2015, 6, 7249–7257.Reactivity of Amido-Digermynes, LGeGeL (L = Bulky Amide), toward Olefins and Related Molecules: Facile Reduction, C−H Activation, and Reversible Cycloaddition of Unsaturated Substrates; Hadlington, T. J., Li, J., Hermann, M., Davey, A., Frenking, G., and Jones C., Organometallics, 2015, 34, 3175–3185.Two-coordinate Hydrido-Germylenes; Hadlington, T. J., Schwarze, B., Izgorodina, E. I., and Jones, C., Chem. Commun., 2015, 51, 6854–6857.Low Coordinate Germanium(II) and Tin(II) Hydride Complexes: Efficient Catalysts for the Hydroboration of Carbonyl Compounds; Hadlington, T. J., Hermann, M., Frenking, G., and Jones, C., J. Am. Chem. Soc., 2014, 136, 3028–3031.A Singly Bonded Amido-Distannyne: H2 Activation and Isocyanide Coordination; T. J. Hadlington and C. Jones, Chem. Commun., 2014, 50, 2321–2323.Synthesis and Characterization of Extremely Bulky Amido-Germanium(II) Halide Complexes; T. J. Hadlington, J. Li, C. Jones, Can. J. Chem., 2014, 92, 427–433.Activation of H2 by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene; T. J. Hadlington, M. Hermann, J. Li, G. Frenking, and C. Jones, Angew. Chem., 2013, 52, 10199–10203; selected as aHot Paper.Synthesis and Crystal Structures of Two Bulky bis(Amido)Germylenes; E. W. Y. Wong, T. J. Hadlington and C. Jones, Main Group Met. Chem., 2013, 36, 133–136.Extremely Bulky Amido and Amidinato Complexes of Boron and Aluminium Halides: Synthesis and Reduction Studies; E. W. Y. Wong, D. Dange, L. Fohlmeister, T. J. Hadlington, and C. Jones, Aust. J. Chem., 2013, 66, 1144–1154.Utilizing Steric Bulk to Stabilize Molybdenum Aminogermylyne and Aminogermylene Complexes; J. Hicks, T. J. Hadlington, C. Schenk, J. Li, and C. Jones, Organometallics, 2013, 32, 323–329.
• Acknowledgements
• Contents
• Abbreviations
• 1 General Introduction
• 2 The Development of Extremely Bulky Amide Ligands and Their Application to the Synthesis of Group 14 Element(II) Halide Complexes
• 3 Synthesis and Reactivity of Heavier Alkyne Analogues Stabilised by Extremely Bulky Amide Ligands
• 4 Reactivity of Low-Coordinate Group 14 Element(II) Hydride Complexes
• 5 Stoichiometric Reactivity and Catalytic Applications of Heavier Tetrylene Derivatives
• 6 The Use of a Bulky Boryl-Substituted Amide Ligand in Low-Oxidation State Group 14 Element Chemistry
• Appendix A: General Synthetic Considerations
• Appendix B Crystallographic Data
• Appendix C: Computational Studies