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Group 13-derived radicals from α-diimines via hydro- and carboalumination reactions

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Bodach,  Alexander
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6;
Research Group Felderhoff, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Felderhoff,  Michael
Research Group Felderhoff, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Bodach, A., Bamford, K. L., Longobardi, L. E., Felderhoff, M., & Stephan, D. W. (2020). Group 13-derived radicals from α-diimines via hydro- and carboalumination reactions. Dalton Transactions, 49(33), 11689-11696. doi:10.1039/D0DT02498H.


Cite as: http://hdl.handle.net/21.11116/0000-0007-19BB-B
Abstract
The mechanochemical synthesis of tertiary and secondary alanes AlR3 (R = Np 1 or Mes 2; HAlR2 R = Np 3 or Mes 4) is described. These species are reacted with several α-diimines to give a series of aluminium-derived radicals of the form [(diimine)AlR2]˙ (6–11). EPR and several crystallographic studies are reported. These species are thought to form via hydro- or carboalumination and subsequent elimination reactions. This view is supported by the structural data for minor products C12H7(NHDipp)(NDipp)AliBu2 5 and C13H8(C(iBu)=N(m-Xy)(NH(m-Xy)))AliBu2 12. In addition, the characterization of (C6F5)B(OC(C6F5)OC12H8) indicates that such a carboboration pathway also provides access to related boron-derived radicals.