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The Resource Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands

Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands

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eng
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1 online resource (214 pages)
Contents
  • Supervisor's Foreword -- Abstract -- Parts of this thesis have been published in the following journal articles:J. Hicks, E. Underhill, C. E. Kefalidis, L. Maron, C. Jones, A Mixed-Valence Tri-Zinc Complex, LZnZnZnL (L = Bulky Amide), Bearing a Linear Chain of Two-Coordinate Zinc Centres, Angew. Chem., Int. Ed., 2015, 54, 10000. Highlighted in Nature Chemistry, Chemistry in Australia and as a Hot Paper in Angew. Chem. Int. Ed.J. Hicks, C. Jones, Low-Coordinate Cobalt(I) Complexes Stabilized by an Extremely Bulky Amide Ligand, Organ -- Acknowledgements -- Declaration -- Contents -- Abbreviations -- Summary of Compounds -- 1 General Introduction -- 1.1 Transition Metals -- 1.2 Low Oxidation State Transition Metal Complexes -- 1.2.1 Bulky Ligands Used into Stabilise Low Oxidation State Complexes -- 1.2.2 Preparation of Low Oxidation State Transition Metal Complexes -- 1.3 Metal-Metal Bonding in Transition Metal Complexes -- 1.3.1 History -- 1.3.2 Quintuple Bonds -- 1.4 Magnesium(I) Complexes -- 1.4.1 Reactivity of Ý-Diketiminate Stabilised Magnesium(I) Complexes -- 1.4.2 Using Ý-Diketiminate Stabilised Magnesium(I) Complexes as Reducing Agents in Inorganic Synthesis -- References -- 2 Extremely Bulky Amido d-Block Metal(II) Halide Complexes -- 2.1 Introduction -- 2.1.1 Previously Reported Bulky Amido Transition Metal(II) Halide Complexes -- 2.1.2 Previously Reported Bulky Amido Group 12 Metal(II) Halide Complexes -- 2.1.3 Terphenyl Stabilised D-Block Metal Halide Complexes -- 2.1.3.1 Terphenyl Transition Metal(II) Halide Complexes -- 2.1.3.2 Terphenyl Group 12 Metal(II) Halide Complexes -- 2.1.4 Extremely Bulky Monodentate Amido Ligands -- 2.2 Research Outline -- 2.3 Results and Discussion -- 2.3.1 Preparation of Bulky Potassium Amide Salts -- 2.3.2 Bulky Amido First Row Transition Metal(II) Halide Complexes
  • 2.3.3 Bulky Amido Group 12 Metal(II) Halide Complexes -- 2.4 Conclusion -- 2.5 Experimental -- References -- 3 Preparation of Low Oxidation State Manganese Complexes Stabilised by Bulky Amide Ligands -- 3.1 Introduction -- 3.1.1 Low Oxidation State Manganese Complexes -- 3.1.1.1 Metal-Metal Bonded Manganese(I) Dimers -- 3.1.1.2 Carbonyl-free Manganese(I) Complexes Without Metal-Metal Bonds -- 3.2 Research Outline -- 3.3 Results and Discussion -- 3.3.1 Preparation and Characterisation of a Two-Coordinate Manganese(I) Dimer with an Unsupported Metal-Metal Bond -- 3.3.2 Preparation and Characterisation of a Two-Coordinate Manganese(0) Heterobimetallic Complex with an Unsupported Mn-Mg Bond -- 3.3.3 Reactivity of a Two-Coordinate Manganese(0) Heterobimetallic Complex -- 3.3.3.1 Reactivity of an Mn-Mg Bonded Complex Towards Inorganic Complexes -- 3.3.3.2 Reactivity of an Mn-Mg Bonded Complex Towards Small Organic Molecules and Gases -- 3.4 Conclusion -- 3.5 Experimental -- References -- 4 Preparation of Low Oxidation State Group 12 Metal Complexes Stabilised by Bulky Amide Ligands -- 4.1 Introduction -- 4.1.1 The First Molecular Compounds Possessing Group 12 Metal-Metal Bonds -- 4.1.2 Isolation of the First Zinc(I) Dimer -- 4.1.3 Other Metal-Metal Bonded Zinc(I) Compounds -- 4.1.3.1 A Homologous Series of Two-Coordinate Group 12 Metal-Metal Bonded Dimers -- 4.1.3.2 Other Recently Reported Low Oxidation State Group 12 Metal Complexes -- 4.2 Research Outline -- 4.3 Results and Discussion -- 4.3.1 Preparation and Characterisation of a Homologous Series of Group 12 Metal(I) Dimers -- 4.3.2 Preparation and Characterisation of a Two-Coordinate Zinc(0) Heterobimetallic Complex with an Unsupported Zn-Mg Bond -- 4.3.3 Attempts to Synthesise Two-Coordinate Cadmium(0) or Mercury(0) Heterobimetallic Complexes with Unsupported M-Mg Bonds
  • 4.3.4 Reactivity of a Two-Coordinate Zinc(0) Heterobimetallic Complex with an Unsupported Zn-Mg Bond -- 4.3.4.1 Preparation and Characterisation of a Homologous Series of Mixed-Valence Group 12 Metal Trimetallic Complexes -- 4.4 Conclusion -- 4.5 Experimental -- References -- 5 Preparation of Low Oxidation State Cobalt Complexes Stabilised by a Bulky Amide Ligand -- 5.1 Introduction -- 5.1.1 Low Oxidation State Cobalt Complexes Stabilised by Bulky Bidentate Monoanionic Ligands -- 5.1.2 Low Oxidation State Cobalt Complexes Stabilised by Bulky Monodentate Monoanionic Ligands -- 5.1.3 Other Relevant Low Coordinate, Low Oxidation State Cobalt Complexes -- 5.2 Research Outline -- 5.3 Results and Discussion -- 5.3.1 Preparation and Characterisation of Two Low Coordinate Amido Cobalt(I) Complexes -- 5.3.2 Reactivity of the Two Amido Cobalt(I) Complexes -- 5.4 Conclusion -- 5.5 Experimental -- References -- 6 Preparation of Molybdenum Aminogermylene and Aminogermylyne Complexes -- 6.1 Introduction -- 6.1.1 Previously Reported Transition Metal Tetrelyne Complexes -- 6.1.1.1 Transition Metal Germylyne Complexes -- 6.1.1.2 Transition Metal Stannylyne Complexes -- 6.1.1.3 Transition Metal Plumbylyne Complexes -- 6.1.1.4 Transition Metal-Silylyne Complexes -- 6.2 Research Outline -- 6.3 Results and Discussion -- 6.3.1 Preparation of Two Molybdenum Aminogermylene Complexes -- 6.3.2 Preparation of a Molybdenum Aminogermylyne Complex -- 6.4 Conclusion -- 6.5 Experimental -- References -- 7 Appendix -- 7.1 General Procedures -- 7.1.1 X-Ray Crystallography -- 7.1.2 Magnetic Susceptibility Measurements -- 7.1.3 EPR Spectroscopy Studies -- 7.1.4 Computational Studies -- 7.2 Miscellaneous Data -- 7.3 Summary of Crystallographic Data -- References
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Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands
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Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands
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eng
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Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands
Label
Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands
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http://libproxy.rpi.edu/login?url=https://ebookcentral.proquest.com/lib/rpi/detail.action?docID=4723615
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rdacarrier
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multicolored
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text
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txt
Content type MARC source
rdacontent
Contents
  • Supervisor's Foreword -- Abstract -- Parts of this thesis have been published in the following journal articles:J. Hicks, E. Underhill, C. E. Kefalidis, L. Maron, C. Jones, A Mixed-Valence Tri-Zinc Complex, LZnZnZnL (L = Bulky Amide), Bearing a Linear Chain of Two-Coordinate Zinc Centres, Angew. Chem., Int. Ed., 2015, 54, 10000. Highlighted in Nature Chemistry, Chemistry in Australia and as a Hot Paper in Angew. Chem. Int. Ed.J. Hicks, C. Jones, Low-Coordinate Cobalt(I) Complexes Stabilized by an Extremely Bulky Amide Ligand, Organ -- Acknowledgements -- Declaration -- Contents -- Abbreviations -- Summary of Compounds -- 1 General Introduction -- 1.1 Transition Metals -- 1.2 Low Oxidation State Transition Metal Complexes -- 1.2.1 Bulky Ligands Used into Stabilise Low Oxidation State Complexes -- 1.2.2 Preparation of Low Oxidation State Transition Metal Complexes -- 1.3 Metal-Metal Bonding in Transition Metal Complexes -- 1.3.1 History -- 1.3.2 Quintuple Bonds -- 1.4 Magnesium(I) Complexes -- 1.4.1 Reactivity of Ý-Diketiminate Stabilised Magnesium(I) Complexes -- 1.4.2 Using Ý-Diketiminate Stabilised Magnesium(I) Complexes as Reducing Agents in Inorganic Synthesis -- References -- 2 Extremely Bulky Amido d-Block Metal(II) Halide Complexes -- 2.1 Introduction -- 2.1.1 Previously Reported Bulky Amido Transition Metal(II) Halide Complexes -- 2.1.2 Previously Reported Bulky Amido Group 12 Metal(II) Halide Complexes -- 2.1.3 Terphenyl Stabilised D-Block Metal Halide Complexes -- 2.1.3.1 Terphenyl Transition Metal(II) Halide Complexes -- 2.1.3.2 Terphenyl Group 12 Metal(II) Halide Complexes -- 2.1.4 Extremely Bulky Monodentate Amido Ligands -- 2.2 Research Outline -- 2.3 Results and Discussion -- 2.3.1 Preparation of Bulky Potassium Amide Salts -- 2.3.2 Bulky Amido First Row Transition Metal(II) Halide Complexes
  • 2.3.3 Bulky Amido Group 12 Metal(II) Halide Complexes -- 2.4 Conclusion -- 2.5 Experimental -- References -- 3 Preparation of Low Oxidation State Manganese Complexes Stabilised by Bulky Amide Ligands -- 3.1 Introduction -- 3.1.1 Low Oxidation State Manganese Complexes -- 3.1.1.1 Metal-Metal Bonded Manganese(I) Dimers -- 3.1.1.2 Carbonyl-free Manganese(I) Complexes Without Metal-Metal Bonds -- 3.2 Research Outline -- 3.3 Results and Discussion -- 3.3.1 Preparation and Characterisation of a Two-Coordinate Manganese(I) Dimer with an Unsupported Metal-Metal Bond -- 3.3.2 Preparation and Characterisation of a Two-Coordinate Manganese(0) Heterobimetallic Complex with an Unsupported Mn-Mg Bond -- 3.3.3 Reactivity of a Two-Coordinate Manganese(0) Heterobimetallic Complex -- 3.3.3.1 Reactivity of an Mn-Mg Bonded Complex Towards Inorganic Complexes -- 3.3.3.2 Reactivity of an Mn-Mg Bonded Complex Towards Small Organic Molecules and Gases -- 3.4 Conclusion -- 3.5 Experimental -- References -- 4 Preparation of Low Oxidation State Group 12 Metal Complexes Stabilised by Bulky Amide Ligands -- 4.1 Introduction -- 4.1.1 The First Molecular Compounds Possessing Group 12 Metal-Metal Bonds -- 4.1.2 Isolation of the First Zinc(I) Dimer -- 4.1.3 Other Metal-Metal Bonded Zinc(I) Compounds -- 4.1.3.1 A Homologous Series of Two-Coordinate Group 12 Metal-Metal Bonded Dimers -- 4.1.3.2 Other Recently Reported Low Oxidation State Group 12 Metal Complexes -- 4.2 Research Outline -- 4.3 Results and Discussion -- 4.3.1 Preparation and Characterisation of a Homologous Series of Group 12 Metal(I) Dimers -- 4.3.2 Preparation and Characterisation of a Two-Coordinate Zinc(0) Heterobimetallic Complex with an Unsupported Zn-Mg Bond -- 4.3.3 Attempts to Synthesise Two-Coordinate Cadmium(0) or Mercury(0) Heterobimetallic Complexes with Unsupported M-Mg Bonds
  • 4.3.4 Reactivity of a Two-Coordinate Zinc(0) Heterobimetallic Complex with an Unsupported Zn-Mg Bond -- 4.3.4.1 Preparation and Characterisation of a Homologous Series of Mixed-Valence Group 12 Metal Trimetallic Complexes -- 4.4 Conclusion -- 4.5 Experimental -- References -- 5 Preparation of Low Oxidation State Cobalt Complexes Stabilised by a Bulky Amide Ligand -- 5.1 Introduction -- 5.1.1 Low Oxidation State Cobalt Complexes Stabilised by Bulky Bidentate Monoanionic Ligands -- 5.1.2 Low Oxidation State Cobalt Complexes Stabilised by Bulky Monodentate Monoanionic Ligands -- 5.1.3 Other Relevant Low Coordinate, Low Oxidation State Cobalt Complexes -- 5.2 Research Outline -- 5.3 Results and Discussion -- 5.3.1 Preparation and Characterisation of Two Low Coordinate Amido Cobalt(I) Complexes -- 5.3.2 Reactivity of the Two Amido Cobalt(I) Complexes -- 5.4 Conclusion -- 5.5 Experimental -- References -- 6 Preparation of Molybdenum Aminogermylene and Aminogermylyne Complexes -- 6.1 Introduction -- 6.1.1 Previously Reported Transition Metal Tetrelyne Complexes -- 6.1.1.1 Transition Metal Germylyne Complexes -- 6.1.1.2 Transition Metal Stannylyne Complexes -- 6.1.1.3 Transition Metal Plumbylyne Complexes -- 6.1.1.4 Transition Metal-Silylyne Complexes -- 6.2 Research Outline -- 6.3 Results and Discussion -- 6.3.1 Preparation of Two Molybdenum Aminogermylene Complexes -- 6.3.2 Preparation of a Molybdenum Aminogermylyne Complex -- 6.4 Conclusion -- 6.5 Experimental -- References -- 7 Appendix -- 7.1 General Procedures -- 7.1.1 X-Ray Crystallography -- 7.1.2 Magnetic Susceptibility Measurements -- 7.1.3 EPR Spectroscopy Studies -- 7.1.4 Computational Studies -- 7.2 Miscellaneous Data -- 7.3 Summary of Crystallographic Data -- References
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