Conformational twisting of a formate-bridged diiridium complex enables catalytic formic acid dehydrogenation. Issue 38 (12th September 2018)

• Record Type: Journal Article
• Authors: Lauridsen, Paul J.; Lu, Zhiyao; Celaje, Jeff J. A.; Kedzie, Elyse A.; Williams, Travis J.
• Is Part Of: Dalton transactions. Volume 47:Issue 38(2018)
• Page Start: 13559
• Page End: 13564
• Publication Date: 2018-09-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt03268h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Catalytic reactivity is switched on for formic acid dehydrogenation by a single precursor's unique ability to form a geometrically twisted dimer. Abstract : We previously reported that iridium complex1a enables the first homogeneous catalytic dehydrogenation of neat formic acid and enjoys unusual stability through millions of turnovers. Binuclear iridium hydride species5a, which features a provocative C 2 -symmetric geometry, was isolated from the reaction as a catalyst resting state. By synthesizing and carefully examining the catalytic initiation of a series of analogues to1a, we establish here a strong correlation between the formation of C2-twisted iridium dimers analogous to5a and the reactivity of formic acid dehydrogenation: an efficient C2 twist appears unique to1a and essential to catalytic reactivity.