C–C Activation in the Solid State in an Organometallic σ-Complex

Herein is reported the synthesis, by a solid-state reaction from [Ir(NBD)2(PiPr3)][BArF4], of the first example of a C–C σ-complex with iridium, [Ir(BINOR-S)(PiPr3)][BArF4]. This compound is unique in that in the solid state it undergoes reversible activation of the C–C single bond that interacts with the metal center, establishing a temperature-dependent equilibrium between Ir(III) C–C σ/Ir(V) bis-alkyl complexes. This process has been interrogated by variable-temperature X-ray diffraction, NMR spectroscopy, and DFT calculations.

本研究报道了以[Ir(NBD)₂(PiPr₃)][BArF₄]为起始原料，通过固相反应合成首例含铱的C–C σ络合物[Ir(BINOR-S)(PiPr₃)][BArF₄]的过程。该化合物具有独特的固态行为：其与金属中心相互作用的C–C单键可发生可逆活化，进而在三价铱的C–C σ络合物与五价铱的双烷基络合物之间建立起温度依赖的动态平衡。本研究通过变温X射线衍射、核磁共振波谱法以及密度泛函理论（DFT）计算对该过程进行了系统探究与解析。