Department of Chemistry and Applied Biosciences ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Str. 10, Zürich CH-8093, Switzerland.
Supramolecular and Homogeneous Catalysis Group, van 't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands.
Nat Commun. 2017 Apr 28;8:14990. doi: 10.1038/ncomms14990.
Small organic molecules provide a promising solution for the requirement to store large amounts of hydrogen in a future hydrogen-based energy system. Herein, we report that diolefin-ruthenium complexes containing the chemically and redox non-innocent ligand tropdad catalyse the production of H from formaldehyde and water in the presence of a base. The process involves the catalytic conversion to carbonate salt using aqueous solutions and is the fastest reported for acceptorless formalin dehydrogenation to date. A mechanism supported by density functional theory calculations postulates protonation of a ruthenium hydride to form a low-valent active species, the reversible uptake of dihydrogen by the ligand and active participation of both the ligand and the metal in substrate activation and dihydrogen bond formation.
小分子为未来氢能体系中大量储存氢气的需求提供了有前景的解决方案。在此，我们报告了二烯烃-钌配合物含有化学和氧化还原非惰性配体 tropdad，在碱的存在下催化甲醛和水生成 H。该过程涉及使用水溶液将其催化转化为碳酸盐盐，是迄今为止报道的接受体无甲醛脱氢反应中最快的。密度泛函理论计算支持的机理假设是质子化钌氢化物形成低价活性物种，配体可逆地吸收氢气，配体和金属都积极参与底物活化和氢键形成。
