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Application of a Donor-Acceptor Strategy to Intercept Molecular Main Group Element Precursors en Route to Nanodimensional Materials

  • Author / Creator
    Swarnakar, Anindya K
  • The work in this thesis describes the stabilization of reactive and elusive main group entities with the aid of Wittig reagents, transition metal complexes, or N-heterocyclic carbenes (NHCs) as donors. Wittig reagents were employed to stabilize various group 14 element dihydrides (EH2; E = Ge and Sn) within donor-acceptor complexes. Furthermore, traditional hot injection or microwave assisted heating of a GeH2 donor-acceptor complex yielded surface functionalized Ge nanoparticles. Donor-acceptor complexes of unsaturated mixed group 13/15 hydrides (HB=NH) were also synthesized via Lewis acid-assisted N2 elimination followed by H- migration from B to N within carbene-bound azidoborane precursors. The reactivity of such HB=NH complexes was studied in detail including attempts to convert these species into bulk BN. Parallel chemistry with Ga was explored in an attempt to prepare a donor-acceptor complex of HGa=NH; however the high reactivity of the Ga-H bonds in the precursor azidogallane complex NHC•GaH2N3 did not permit the isolation of such species. In addition, donor-acceptor complexes of chlorooxoborane (ClBO) featuring very short B=O bonds have been synthesized. These species are found to be active reagents for alkane C-F bond activation and functionalization.

  • Subjects / Keywords
  • Graduation date
    Fall 2017
  • Type of Item
    Thesis
  • Degree
    Doctor of Philosophy
  • DOI
    https://doi.org/10.7939/R3DV1D467
  • License
    This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
  • Language
    English
  • Citation for previous publication
    • Swarnakar, A. K.; Hering-Junghans, C.; Nagata, K.; Ferguson, M. J.; McDonald, R.; Tokitoh, N.; Rivard, E. Angew. Chem. Int. Ed. 2015, 54, 10666.
    • Swarnakar, A. K.; Ferguson, M. J.; McDonald, R.; Rivard, E. Dalton Trans. 2016, 45, 6071.
    • Swarnakar, A. K.; Hering-Junghans, C.; Ferguson, M. J.; McDonald, R.; Rivard, E. Chem. Sci. 2017, 8, 2337.
    • Swarnakar, A. K.; McDonald, S. M.; Deutsch, K. C.; Choi, P.; Ferguson, M. J.; McDonald, R.; Rivard, E. Inorg. Chem. 2014, 53, 8662.
    • Swarnakar, A. K.; Ferguson, M. J.; McDonald, R.; Rivard, E. Dalton Trans. 2017, 46, 1406.
    • Purkait, T. K.; Swarnakar, A. K.; De Los Reyes, G. B.; Hegmann, F. A.; Rivard, E.; Veinot, J. G. C. Nanoscale 2015, 7, 2241.
  • Institution
    University of Alberta
  • Degree level
    Doctoral
  • Department
  • Supervisor / co-supervisor and their department(s)