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

Alexander Bodach; Karlee L Bamford; Lauren E Longobardi; Michael Felderhoff; Douglas W Stephan

doi:10.1039/d0dt02498h

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

Dalton Trans. 2020 Aug 25;49(33):11689-11696. doi: 10.1039/d0dt02498h.

Authors

Alexander Bodach¹, Karlee L Bamford², Lauren E Longobardi², Michael Felderhoff³, Douglas W Stephan²

Affiliations

¹ Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6. dstephan@chem.utoronto.ca and Max-Planck-Institut für Kohlenforschung, Department of Heterogeneous Catalysis, Kaiser-Wilhelm-Platz 1, 45470 Muelheim an der Ruhr, Germany.
² Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6. dstephan@chem.utoronto.ca.
³ Max-Planck-Institut für Kohlenforschung, Department of Heterogeneous Catalysis, Kaiser-Wilhelm-Platz 1, 45470 Muelheim an der Ruhr, Germany.

PMID: 32789402
DOI: 10.1039/d0dt02498h

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)AliBu25 and C13H8(C(iBu)[double bond, length as m-dash]N(m-Xy)(NH(m-Xy)))AliBu212. In addition, the characterization of (C6F5)2B(OC(C6F5)OC12H8) indicates that such a carboboration pathway also provides access to related boron-derived radicals.