Application of beta-Diketiminato Arene-Substituted Ru(II) Complexes in Highly Efficient H-2 Dehydrocoupling of Amine Boranes

作者：Schreiber Dominique F; O' Connor Crystal; Grave Christian; Ortin Yannick; Mueller Bunz Helge; Phillips Andrew D^*

来源：ACS Catalysis, 2012, 2(12): 2505-2511.

DOI：10.1021/cs300499d

• ammonia borane
• N,N-dimethylamine borane
• dehydrocoupling
• ruthenium(II) beta-diketiminato complexes
• hydrogen generation

Amine borane type substrates show significant potential as safe and effective chemical hydrogen storage materials. beta-Diketiminato(eta(6)-arene)-Ru(II) complexes have shown the ability to rapidly perform the heterolytic cleavage of H-2 under mild conditions through bifunctional metal-ligand interaction. The presented work explores the applicability of such complexes toward the catalytic dehydrogenation of different substituted amine boranes, in particular, ammonia borane (AB) and N,N-dimethylamine borane (DMAB). Complex [(eta(6)-C6H6)-Ru(2,6-(CH3)(2)-C6H3NC(CH3))(2)CH]OTf (1) showed excellent activity in the catalytic release of a single equivalent of H-2 within 0.5 h from a concentrated DMAB solution in THF (3.2 M) at near ambient temperatures. Studies involving structural analogues of 1 allowed insight into the operational dehydrocoupling mechanism. It is concluded from this preliminary work that in solution, 1 forms a homogeneous bifunctional active species that does not undergo deactivation, even after prolonged exposure to H2 at elevated pressures.

• 出版日期2012-12