通过具有半不稳定膦的吡啶二亚胺配体的氧化还原控制实现CO和NO的顺序脱氧
Sequential Deoxygenation of CO and NO via Redox-Control of a Pyridinediimine Ligand with a Hemilabile Phosphine.
作者信息
Lewine Hanalei R, Teigen Allison G, Trausch April M, Lindblom Kaitlyn M, Seda Takele, Reinheimer Eric W, Kowalczyk Tim, Gilbertson John D
机构信息
Department of Chemistry, Western Washington University, Bellingham, Washington98225, United States.
Department of Physics, Western Washington University, Bellingham, Washington98225, United States.
出版信息
Inorg Chem. 2023 Sep 18;62(37):15173-15179. doi: 10.1021/acs.inorgchem.3c02323. Epub 2023 Sep 5.
The deoxygenation of environmental pollutants CO and NO to form value-added products is reported. CO reduction with subsequent CO release and NO conversion to NO are achieved via the starting complex Fe(PDI)Cl (). contains the redox-active pyridinediimine (PDI) ligand with a hemilabile phosphine located in the secondary coordination sphere. was reduced with SmI under a CO atmosphere to form the direduced monocarbonyl Fe(PDI)(CO) (). Subsequent CO release was achieved via oxidation of using the NO source, NO. The resulting [Fe(PDI)(NO)] () mononitrosyl iron complex (MNIC) is formed as the exclusive reduction product due to the hemilabile phosphine. was investigated computationally to be characterized as {FeNO}, an unusual intermediate-spin Fe(III) coupled to triplet NO and a singly reduced PDI ligand.
据报道，环境污染物一氧化碳（CO）和一氧化氮（NO）脱氧可形成增值产品。通过起始配合物Fe(PDI)Cl（）实现了CO的还原以及随后的CO释放和NO向NO的转化。 包含具有位于二级配位球中的半不稳定膦的氧化还原活性吡啶二亚胺（PDI）配体。 在CO气氛下用SmI将 还原以形成双还原单羰基Fe(PDI)(CO)（）。随后通过使用NO源NO氧化 实现了CO的释放。由于半不稳定膦的存在，所得的[Fe(PDI)(NO)]（）单亚硝酰铁配合物（MNIC）作为唯一的还原产物形成。 通过计算研究 以表征为{FeNO}，这是一种不寻常的中间自旋Fe(III)，与三重态NO和单还原的PDI配体偶联。
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