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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., Tir; Acknowledgements; Contents; Abbreviations
1 General Introduction1.1 Low-Oxidation State Main-Group Chemistry; 1.2 Oxidation States and the Inert-Pair Effect; 1.2.1 Bonding in the Heavier Ditetrelenes; 1.2.2 Bonding in the Heavier Ditetrylynes; 1.2.3 Kinetic Stabilisation; 1.2.4 Accessing Low-Oxidation State Main-Group Complexes; 1.2.4.1 Salt-Metathesis with Low-Oxidation State Halide Sources; 1.2.4.2 Reduction of Element Halide Precursors; References; 2 The Development of Extremely Bulky Amide Ligands and Their Application to the Synthesis of Group 14 Element(II) Halide Complexes; 2.1 Introduction
2.1.1 The Use of Sterically Demanding Chelating Ligands in Group 14 Element(II) Chemistry2.1.2 The Use of Sterically Demanding Monodentate Ligands in Group 14 Element(II) Chemistry; 2.2 Research Proposal; 2.3 Results and Discussion; 2.3.1 Synthesis of Extremely Bulky Secondary Amines; 2.3.1.1 Extremely Bulky Anilines; 2.3.1.2 Extremely Bulky Aryl-Silyl Amines; 2.3.1.3 Extremely Bulky Bis(aryl) Amines; 2.3.2 Synthesis of Group 14 Element(II) Halide Complexes; 2.3.2.1 Aryl-Silyl Amido Group 14 Element(II) Halide Complexes; 2.3.2.2 Bis(aryl) Amido Group 14 Element(II) Halide Complexes
2.4 Conclusion2.5 Experimental; References; 3 Synthesis and Reactivity of Heavier Alkyne Analogues Stabilised by Extremely Bulky Amide Ligands; 3.1 Introduction; 3.1.1 Silicon Analogues of Alkynes; 3.1.1.1 Synthesis and Reactivity of 2-Coordinate Disilynes; 3.1.2 Germanium Analogues of Alkynes; 3.1.2.1 Synthesis of 2-Coordinate Digermynes; 3.1.2.2 Reactivity of 2-Coordiante Digermynes Towards H2 and Lewis-Bases; 3.1.2.3 Reactions of 2-Coordinate Digermynes with Unsaturated Molecules and Olefin Activation/Addition; N-N Unsaturates; Alkynes; Linear Alkenes; Cycloalkenes
3.1.3 Tin Analogues of Alkynes3.1.3.1 Synthesis of 2-Coordinate Distannynes; 3.1.3.2 Reactivity of 2-Coordinate Distannynes; 3.1.4 Lead Analogues of Alkynes; 3.1.4.1 Synthesis and Reactivity of a 2-Coordinate Diplumbyne; 3.1.5 Low-Oxidation State Group 14 Element Hydride Complexes; 3.1.5.1 Parent Heavier Methylenes; 3.1.5.2 Di-nuclear Low-Oxidation State Group 14 Element Hydride Complexes; 3.1.5.3 Monomeric Low-Oxidation State Group 14 Element Hydride Complexes; Monomeric Silicon (II) Hydride Complexes; Monomeric Germanium(II) Hydride Complexes; Monomeric Tin(II) Hydride Complexes
1 General Introduction1.1 Low-Oxidation State Main-Group Chemistry; 1.2 Oxidation States and the Inert-Pair Effect; 1.2.1 Bonding in the Heavier Ditetrelenes; 1.2.2 Bonding in the Heavier Ditetrylynes; 1.2.3 Kinetic Stabilisation; 1.2.4 Accessing Low-Oxidation State Main-Group Complexes; 1.2.4.1 Salt-Metathesis with Low-Oxidation State Halide Sources; 1.2.4.2 Reduction of Element Halide Precursors; References; 2 The Development of Extremely Bulky Amide Ligands and Their Application to the Synthesis of Group 14 Element(II) Halide Complexes; 2.1 Introduction
2.1.1 The Use of Sterically Demanding Chelating Ligands in Group 14 Element(II) Chemistry2.1.2 The Use of Sterically Demanding Monodentate Ligands in Group 14 Element(II) Chemistry; 2.2 Research Proposal; 2.3 Results and Discussion; 2.3.1 Synthesis of Extremely Bulky Secondary Amines; 2.3.1.1 Extremely Bulky Anilines; 2.3.1.2 Extremely Bulky Aryl-Silyl Amines; 2.3.1.3 Extremely Bulky Bis(aryl) Amines; 2.3.2 Synthesis of Group 14 Element(II) Halide Complexes; 2.3.2.1 Aryl-Silyl Amido Group 14 Element(II) Halide Complexes; 2.3.2.2 Bis(aryl) Amido Group 14 Element(II) Halide Complexes
2.4 Conclusion2.5 Experimental; References; 3 Synthesis and Reactivity of Heavier Alkyne Analogues Stabilised by Extremely Bulky Amide Ligands; 3.1 Introduction; 3.1.1 Silicon Analogues of Alkynes; 3.1.1.1 Synthesis and Reactivity of 2-Coordinate Disilynes; 3.1.2 Germanium Analogues of Alkynes; 3.1.2.1 Synthesis of 2-Coordinate Digermynes; 3.1.2.2 Reactivity of 2-Coordiante Digermynes Towards H2 and Lewis-Bases; 3.1.2.3 Reactions of 2-Coordinate Digermynes with Unsaturated Molecules and Olefin Activation/Addition; N-N Unsaturates; Alkynes; Linear Alkenes; Cycloalkenes
3.1.3 Tin Analogues of Alkynes3.1.3.1 Synthesis of 2-Coordinate Distannynes; 3.1.3.2 Reactivity of 2-Coordinate Distannynes; 3.1.4 Lead Analogues of Alkynes; 3.1.4.1 Synthesis and Reactivity of a 2-Coordinate Diplumbyne; 3.1.5 Low-Oxidation State Group 14 Element Hydride Complexes; 3.1.5.1 Parent Heavier Methylenes; 3.1.5.2 Di-nuclear Low-Oxidation State Group 14 Element Hydride Complexes; 3.1.5.3 Monomeric Low-Oxidation State Group 14 Element Hydride Complexes; Monomeric Silicon (II) Hydride Complexes; Monomeric Germanium(II) Hydride Complexes; Monomeric Tin(II) Hydride Complexes