Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes: Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes
Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes: Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes
复制标题
❀X 配体对 Re(pyridylNHC-CF 3 )(CO) 3 X 配合物光催化还原 CO 2 为 CO 的影响：❀X 配体对 CO 2 光催化还原为 CO 的影响
DOI：
10.1002/ejic.202000283
复制
发表时间：
2020
影响因子：
2.3
通讯作者：
Delcamp, Jared H.
中科院分区：
文献类型：
--
作者：
Shirley, Hunter;Sexton, Thomas More;Liyanage, Nalaka P.;Palmer, C. Zachary;McNamara, Louis E.;Hammer, Nathan I.;Tschumper, Gregory S.;Delcamp, Jared H.
合成了一系列五种 Re(pyNHC-芳基)(CO)3X 配合物，其中 pyNHC 是吡啶基 N-杂环卡宾，并通过 NMR、UV/Vis 吸收光谱、IR、质谱、时间相关单光子计数、计算分析和循环伏安法进行表征。使用模拟太阳光谱 (AM 1.5G) 评估这些配合物在牺牲电子供体存在下将 CO2 光催化还原为 CO 的情况。 Br 和 CH3CN 作为“X”配体的比较显示出相同的光催化活性（均为 32 TON）。 Cl、NCS 和 P(OEt)3“X”配体的使用都会导致 P(OEt)3 配合物的反应活性降低至 2 TON。这些结果通过“X”解离和激发态寿命测量的计算分析得到合理化。这些结果强调了“X”配体选择对 Re-pyNHC 复合物催化的重要性。
A series of five Re(pyNHC‐aryl)(CO)3X complexes varying the “X” ligand where pyNHC is a pyridyl N‐heterocyclic carbene have been synthesized and characterized through NMR, UV/Vis absorption spectroscopy, IR, mass spectrometry, time‐correlated single photon counting, computational analysis, and cyclic voltammetry. The photocatalytic reduction of CO2to CO in the presence of a sacrificial electron donor with these complexes is evaluated using a simulated solar spectrum (AM 1.5G). Comparison of Br and CH3CN as the “X” ligand shows the same photocatalytic activity (both 32 TON). The use of Cl, NCS and P(OEt)3“X” ligands all led to diminished reactivity with as little as 2 TON for the P(OEt)3complex. These results were rationalized through computational analysis of “X” dissociation and excited‐state lifetime measurements. These results highlight the importance of the “X” ligand selection on catalysis with Re‐pyNHC complexes.