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.
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