Zirconium-Catalyzed Amine Borane Dehydrocoupling and Transfer Hydrogenation

• Published in: Organometallics 2015-10, Vol.34 (19), p.4693-4699
• Main Authors: Erickson, Karla A, Stelmach, John P. W, Mucha, Neil T, Waterman, Rory
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.5b00415

κ5-(Me3SiNCH2CH2)2N­(CH2CH2NSiMe2CH2)Zr (1) has been found to dehydrocouple amine borane substrates, RR′NHBH3 (R = R′ = Me; R = t Bu, R′ = H; R = R′ = H), at low to moderate catalyst loadings (0.5–5 mol %) and good to excellent conversions, forming mainly borazine and borazane products. Other zirconium catalysts, (N3N)­ZrX [(N3N) = N­(CH2CH2NSiMe2CH2)3, X = NMe2 (2), Cl (3), and O t Bu (4)], were found to exhibit comparable activities to that of 1. Compound 1 reacts with Me2NHBH3 to give (N3N)­Zr­(NMe2BH3) (5), which was structurally characterized and features an η2 B–H σ-bond amido borane ligand. Because 5 is unstable with respect to borane loss to form 2, rather than β-hydrogen elimination, and 2–4 do not exhibit X ligand loss during catalysis, dehydrogenation is hypothesized to proceed via an outer-sphere-type mechanism. This proposal is supported by the catalytic hydrogenation of alkenes by 2 using amine boranes as the sacrificial source of hydrogen.