Hydrogenation of CO2 by a Bifunctional PC(sp3)P Iridium(III) Pincer Complex Equipped with Tertiary Amine as a Functional Group

Abstract

AbstractReversible hydrogen storage in the form of stable and mostly harmless chemical substances such as formic acid (FA) is a cornerstone of a fossil fuels‐free economy. In the past, we have reported a primary amine‐functionalized bifunctional iridium(III)‐PC(sp3)P pincer complex as a mild and chemoselective catalyst for the additive‐free decomposition of neat formic acid. In this manuscript, we report on the successful application of a redesigned complex bearing tertiary amine functionality as a catalyst for mild hydrogenation of CO2 to formic acid. The catalyst demonstrates TON up to 6×104 and TOF up to 1.7×104 h−1. In addition to the practical value of the catalyst, experimental and computational mechanistic studies provide the rationale for the design of improved next‐generation catalysts.