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

• DOI: 10.1002/anie.201207903
• Publication Date: 2012-11-29T18:30:12Z
• Authors: Holger Helten; Barnali Dutta; James R. Vance; Matthew E. Sloan; Mairi F. Haddow; Stephen Sproules; David Collison; George R. Whittell; Guy C. Lloyd‐Jones; Ian Manners
• Keywords: phosphine-boranes; AMMONIA-BORANE; Metallocenes; amine-boranes; Amine-boranes; AMIDOBORANE COMPLEXES; PHOSPHINE-BORANE; Transition metals; metallocenes; MOLECULAR-WEIGHT POLYAMINOBORANES; 540; Phosphine-boranes; 01 natural sciences; transition metals; CATALYTIC DEHYDROCOUPLING/DEHYDROGENATION; 0104 chemical sciences; CENTERS; ADDUCTS; dehydrogenation; TRANSITION-METAL; FREE HYDROGEN-TRANSFER; Dehydrogenation

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 Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates.