Low-Valent Main Group Complexes and their Transition Metal-like Reactivity

• Author / Creator

  Roy, Matthew M. D.

• The work presented in this thesis describes the isolation of novel low-valent Group 12 and p-block element-containing molecules. Some of these molecules are shown to exhibit reactivity which mimics that of the transition metals; specifically, with respect to strong bond activation and catalysis. In order to isolate these reactive main group compounds, several stabilization strategies were employed. Lewis base stabilization using bulky N-heterocyclic carbene (NHC) ligands proved to be highly valuable in the formation of
  reactive sites involving electropositive elements. Using NHCs, both cadmium and germanium-based molecules are shown to be active ketone reduction catalysts. Additionally, an extremely bulky NHC ligand was synthesized and demonstrated to stabilize low-coordinate inorganic cations of silver, thallium and germanium. Finally, a bulky anionic (vinylic) donor based on an N-heterocyclic carbene framework proved to be highly effective in the stabilization of low-coordinate, reduced main group environments. This includes the synthesis of two-coordinate silicon compounds which, at the present time, are still exceedingly rare owing to their high degree of reactivity. One such species is shown to cleave strong organic and inorganic σ-bonds, thus demonstrating transition metal-like reactivity with the 2nd most abundant element in the Earth’s crust.

• Subjects / Keywords

  • catalysis
  • silicon
  • bond activation
  • n-heterocyclic carbene
  • vinyl
  • low-valent
  • main group
  • chemistry
  • germanium

• Graduation date

  Fall 2019

• Type of Item

  Thesis

• Degree

  Doctor of Philosophy

• DOI

  https://doi.org/10.7939/r3-2ayd-v829

• License

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