摘要
To achieve efficient catalytic hydrogenation of CO_(2)to formate,we employed a transmetallation strategy to develop three novel iridium(Ⅰ)complexes,which feature N‑heterocyclic carbene‑nitrogen‑phosphine ligands(CNP)and a 1,5‑cyclooctadiene(cod)molecule:[Ir(cod)(κ^(3)‑CN^(im)P)]Cl(1⁃Cl),[Ir(cod)(κ^(3)‑CN^(im)P)]PF6(1⁃PF_(6)),and[Ir(cod)(κ^(3)‑CNHP)]Cl(2).The^(1)H NMR spectra,^(31)P NMR spectra,and high‑resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)‑CNP complexes.Furthermore,single‑crystal X‑ray diffraction analysis confirms the coordination geometry of 1⁃PF_(6).The strong Ir—C(NHC)bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strongσ‑donating ability,which helps stabilize the active metal species during CO_(2)hydrogenation.As a result,the Ir(Ⅰ)‑CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO_(2)to formate,reaching a turnover number(TON)of 1.16×10^(6)after 150 h at a high temperature of 170℃,which was a relatively high value among all the Ir complexes.CCDC:2384071,1⁃PF_(6).
为实现CO_(2)的高效催化加氢制甲酸盐,我们采用转金属化法开发了3种新型铱(Ⅰ)配合物[Ir(cod)(κ^(3)‑CN^(im)P)]Cl(1-Cl)、[Ir(cod)(κ^(3)‑CN^(im)P)]PF_(6)(1-PF_(6))和[Ir(cod)(κ^(3)-CNHP)]Cl(2),它们含有N-杂环卡宾氮膦配体(CNP)和1,5-环二烯(cod)配体。^(1)H NMR谱、^(31)P NMR谱和高分辨率质谱证实了成功合成这3种Ir(Ⅰ)-CNP配合物。单晶X射线衍射分析证实了1-PF_(6)的配位几何结构。强Ir—C(NHC)键表明,由于卡宾碳的强σ电子给予能力,卡宾碳能锚定铱金属中心,这有助于在CO_(2)加氢反应中稳定活性金属物种。结果表明,Ir(Ⅰ)-CNP配合物在CO_(2)加氢生成甲酸盐的反应中表现出显著的催化活性和长寿命,在170℃高温下反应150h,转化数(TON)高达1.16×10^(6),这在所有Ir配合物中是一个相对较高的值。
出处
《无机化学学报》
北大核心
2025年第12期2609-2620,共12页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金(No.22105133)
四川省自然科学基金(No.2023NSFSC1085)
国家留学基金委、国家市场监督管理总局科技项目(No.2022MK111)
中央高校基本科研业务费、内江科技计划项目(No.NJJH202312,NJJH202314,NJJH202328)
内江师范学院重点项目(No.2024ZDZ07)资助。
