Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes


  • This work was supported by the EPSRC, including the UK National EPR Service at The University of Manchester. H. Helten and B. Dutta thank the German Research Foundation (DFG) and the Swiss National Science Foundation (SNSF), respectively, for postdoctoral fellowships. GCLJ is the recipient of a Royal Society Wolfson Research Merit Award.


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Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine–boranes, such as Me2NH⋅BH3 (see scheme). Such TiIII–amidoborane complexes are generated in [Cp2Ti]-catalyzed amine–borane dehydrocoupling reactions, for which diamagnetic MII and MIV species have been previously postulated as precatalysts and intermediates.