Open AccessEfficient Base-Free Aqueous Reforming of Methanol Homogeneously Catalyzed by Ruthenium Exhibiting a Remarkable Acceleration by Added Catalytic Thiol
Author(s) -
Jie Luo,
Sayan Kar,
Michael Rauch,
Michael Montag,
Yehoshoa BenDavid,
David Milstein
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c09007
Subject(s) - chemistry , ruthenium , catalysis , methanol , thiol , aqueous solution , reactivity (psychology) , base (topology) , homogeneous catalysis , combinatorial chemistry , organic chemistry , medicine , mathematical analysis , alternative medicine , mathematics , pathology
Production of H 2 by methanol reforming is of particular interest due the low cost, ready availability, and high hydrogen content of methanol. However, most current methods either require very high temperatures and pressures or strongly rely on the utilization of large amounts of base. Here we report an efficient, base-free aqueous-phase reforming of methanol homogeneously catalyzed by an acridine-based ruthenium pincer complex, the activity of which was unexpectedly improved by a catalytic amount of a thiol additive. The reactivity of this system is enhanced by nearly 2 orders of magnitude upon addition of the thiol, and it can maintain activity for over 3 weeks, achieving a total H 2 turnover number of over 130 000. On the basis of both experimental and computational studies, a mechanism is proposed which involves outer-sphere dehydrogenations promoted by a unique ruthenium complex with thiolate as an assisting ligand. The current system overcomes the need for added base in homogeneous methanol reforming and also highlights the unprecedented acceleration of catalytic activity of metal complexes achieved by the addition of a catalytic amount of thiol.