American Chemical Society
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A Bifunctional Iridium Catalyst Modified for Persistent Hydrogen Generation from Formic Acid: Understanding Deactivation via Cyclometalation of a 1,2-Diphenylethylenediamine Motif

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journal contribution
posted on 2017-05-24, 00:00 authored by Asuka Matsunami, Shigeki Kuwata, Yoshihito Kayaki
Thermal degradation of a bifunctional Ir complex with a 1,2-diphenylethylenediamine (DPEN) framework was investigated, which is relevant to catalyst deactivation in the acceptorless dehydrogenation of formic acid. The well-defined hydridoiridium complex 1b, derived from N-triflyl-1,2-diphenylethylenediamine (TfDPEN), proved to be solely transformed at the reflux temperature of 1,2-dimethoxyethane (DME) into two iridacycles (2 and 3) via C–H bond cleavage at the ortho carbon atoms of the phenyl substituents on the diamine backbone. These products were successfully isolated and characterized by NMR, elemental analysis, and X-ray crystallography. The iridacycle formation was significantly enhanced in the presence of water, possibly due to facile deprotonative orthometalation via a hydroxidoiridium intermediate. To prevent the deactivation process caused by the cyclometalation of the DPEN moiety, a hydridoiridium complex (5b) without phenyl substituents was synthesized from N-triflylethylenediamine (TfEN). The modified complex 5b showed a pronounced ability to catalyze hydrogen evolution from formic acid in a 1/1 mixed solvent of water and DME even in the absence of base additives. The initial rate was maintained for a longer time relative to 1b, and thus formic acid was mostly converted within 80 min under the conditions of a HCOOH/5b ratio of 15900 at 60 °C.