A Simple Route to Difluorocarbene and Perfluoroalkylidene Complexes of Iridium

Primary perfluoroalkyl compounds of iridium undergo facile two-electron reduction to afford a simple route to difluorocarbene and perfluoroalkylidene complexes, two of which have been crystallographically characterized. Low-temperature protonation reactions illustrate that the thermodynamic site of protonation depends on the nature of the fluorinated carbene; the difluorocarbene complex undergoes protonation at iridium, while its perfluoroethylidene congener undergoes protonation at carbon.

铱的伯全氟烷基化合物可发生便捷的两电子还原反应，通过该途径可简便合成二氟卡宾（difluorocarbene）与全氟亚烷基配合物（perfluoroalkylidene complexes），其中两种该类配合物已通过晶体学表征。低温质子化实验表明，质子化的热力学位点取决于氟化卡宾的结构特性：二氟卡宾配合物的质子化发生于铱原子位点，而其全氟乙亚烷基同系物的质子化则发生于碳原子位点。