Martínez-Visiedo Joel, Ibáñez Susana, Gusev Dmitry G, Poyatos Macarena, Peris Eduardo
Institute of Advanced Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I, Av. Vicente Sos Baynat s/n, Castellón E-12071, Spain.
Department of Chemistry and Biochemistry, Wilfrid Laurier University, 75 University Avenue West, Waterloo, Ontario N2L 3C5, Canada.
Inorg Chem. 2025 Apr 28;64(16):8250-8260. doi: 10.1021/acs.inorgchem.5c00534. Epub 2025 Apr 15.
We describe the synthesis of two rhodium and iridium complexes featuring a di-NHC macrocyclic ligand, which incorporates both a diphenylene moiety and a naphthalenediimide (NDI) unit. We observed that the addition of fluoride or chloride resulted in substantial alterations to the steric and electronic properties of both complexes. Specifically, fluoride addition led to the reduction of the NDI unit through the formation of an (OH) NDI intermediate, while chloride produced a (Cl)···NDI adduct. Both adducts were confirmed by mass spectrometry. The impact of fluoride and chloride addition on the steric and electronic properties of the rhodium and iridium NDI-containing complexes was examined using spectroscopic and computational methods. The presence of either halide significantly enhanced the catalytic activity of the complexes in the hydroboration of terminal alkenes. Finally, we demonstrated that this catalytic enhancement is reversible, with the catalytic process being activated and deactivated by the sequential introduction of excess halide and NOBF. This observation reveals a rare example of a halide-induced redox-switchable catalytic (HIRSC) system.
我们描述了两种具有双氮杂环卡宾大环配体的铑和铱配合物的合成，该配体同时包含一个二亚苯基部分和一个萘二亚胺（NDI）单元。我们观察到，添加氟化物或氯化物会导致两种配合物的空间和电子性质发生显著变化。具体而言，添加氟化物通过形成（OH）NDI中间体导致NDI单元的还原，而氯化物则产生（Cl）···NDI加合物。两种加合物均通过质谱法得到证实。使用光谱和计算方法研究了添加氟化物和氯化物对含铑和铱NDI配合物的空间和电子性质的影响。任何一种卤化物的存在都显著增强了配合物在末端烯烃硼氢化反应中的催化活性。最后，我们证明了这种催化增强是可逆的，催化过程通过依次引入过量卤化物和NOBF而被激活和失活。这一观察结果揭示了一个罕见的卤化物诱导的氧化还原可切换催化（HIRSC）系统的例子。
