Corona Helena, Pérez-Jiménez Marina, de la Cruz-Martínez Felipe, Fernández Israel, Campos Jesús
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC), Avenida Américo Vespucio 49, 41092, Sevilla, Spain.
Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain.
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202207581. doi: 10.1002/anie.202207581. Epub 2022 Aug 29.
Bimetallic motifs mediate the selective activation and functionalization of CO in metalloenzymes and some recent synthetic systems. In this work, we build on the nascent concept of bimetallic frustrated Lewis pairs (FLPs) to investigate the activation and reduction of CO . Using the Fe fragment [(depe) Fe] (depe=1,2-bis(diethylphosphino)ethane) as base, we modify the nature of the partner Lewis acid to accomplish a divergent and highly chemoselective reactivity towards CO . [Au(PMe Ar)] irreversibly dissociates CO , Zn(C F ) and B(C F ) yield different CO adducts stabilized by push-pull interactions, while Al(C F ) leads to a rare heterobimetallic C-O bond cleavage, and thus to contrasting reduced products after exposure to dihydrogen. Computational investigations provide a rationale for the divergent reactivity, while Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method substantiates the heterobimetallic bonding situation.
双金属基序介导金属酶和一些近期合成体系中CO的选择性活化和官能团化。在这项工作中，我们基于双金属受阻路易斯对（FLP）的新兴概念来研究CO的活化和还原。以铁片段[(depe)Fe]（depe = 1,2 - 双（二乙基膦基）乙烷）为碱，我们改变配对路易斯酸的性质，以实现对CO的不同且高度化学选择性的反应性。[Au(PMe₃Ar)]不可逆地使CO解离，Zn(C₆F₅)₂和B(C₆F₅)₃产生通过推拉相互作用稳定的不同CO加合物，而Al(C₆F₅)₃导致罕见的异双金属C - O键断裂，从而在暴露于氢气后产生对比鲜明的还原产物。计算研究为不同的反应性提供了理论依据，而能量分解分析 - 化学价自然轨道（EDA - NOCV）方法证实了异双金属键合情况。
