Fixation of Carbon Dioxide with Hydrogen Using Organomotallic Hydride Complexes under Atmospheric Pressure in Water

利用异核铱钌配合物(1)作为催化剂，在室温下，甲酸（HCOOH）的ph选择性分解导致了氢的高效生成。氢同位素气体（HD和/或D2）分别用氘化甲酸（DCOOH）或D2O代替HCOOH或H2O选择性生成。发现配合物1在室温下与甲酸在曝气水中作为四电子还原O2的有效催化剂。在可见光照射下，[Ru(bpy)3]2+（bpy = 2,2′-联吡啶）和抗坏血酸的水溶液在室温下发生光催化析氢。以[C，N]环金属化有机铱配合物为催化剂，在常温常压下的水中实现了H2与甲酸的相互转化，同时伴有co2的排放和固定。

The pH-selective decomposition of formic acid (HCOOH) leading to efficient generation of hydrogen was achieved at room temperature in deaerated water using a heterodinuclear iridium-ruthenium complex (1) as a catalyst. Hydrogen isotopic gases (HD and/or D2) were selectively generated using deuterated formic acid (DCOOH) or D2O in place of HCOOH or H2O, respectively. The complex 1 is found to act as an efficient catalyst for four-electron reduction of O2 with formic acid at room temperature in aerated water. Photocatalytic hydrogen evolution occurs at room temperature under visible-light irradiation of an aqueous solution of [Ru(bpy)3]2+(bpy = 2,2’-bipyridine) and ascorbic acid in the presence of 1. Interconversion between H2 and formic acid accompanied by CO2emission and fixation has been made possible in water at ambient temperature under atmospheric pressure by using a [C,N] cyclometallated organoiridium complex as an efficient catalyst for both directions depending on pH.