Torstensen Kristian, Sixt Florian, Alemayehu Abraham B, Settineri Nicholas S, Ghosh Abhik
Department of Chemistry, University of Tromsø, Tromsø N-9037, Norway.
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720-8229, United States.
Inorg Chem. 2025 May 19;64(19):9621-9630. doi: 10.1021/acs.inorgchem.5c00598. Epub 2025 May 4.
A number of Group 6 metallobiscorrole sandwich compounds with square-antiprismatic coordination were separated into diastereomers by means of careful preparative thin-layer chromatography. The diastereomers differ with respect to the relative orientation of the corrole macrocycles, which are rotated approximately ± 45° or ± 135° relative to each other. The most clear-cut results were obtained for two tungsten corroles, W[TBCFPC] {TBCFPC = -tris[3,5-bis(trifluoromethyl)phenyl]corrolato} and W[TDOMePC] [TDOMePC = -tris(3,5-dimethoxyphenyl)corrolato], for which single-crystal X-ray structures were obtained for the 135° diastereomer; the existence of the 45° diastereomer was inferred by elimination and with support from DFT calculations. For Mo[TBCFPC] and W[TBCFPC], both diastereomers were also fully characterized spectroscopically and their H NMR spectra were essentially fully assigned. The fact that each diastereomer is chiral and exists as two enantiomers (which was previously demonstrated for the 135° form of a tungsten biscorrole) establishes the doubly stereogenic nature of the metallobiscorrole framework - to our knowledge, the first such demonstration for a sandwich compound.
通过仔细的制备型薄层色谱法，将一些具有方形反棱柱配位的第6族金属双卟啉夹心化合物分离为非对映异构体。这些非对映异构体在卟啉大环的相对取向上有所不同，它们彼此相对旋转约±45°或±135°。对于两种钨卟啉W[TBCFPC] {TBCFPC = -三[3,5-双(三氟甲基)苯基]卟啉}和W[TDOMePC] [TDOMePC = -三(3,5-二甲氧基苯基)卟啉]，得到了最明确的结果，其中获得了135°非对映异构体的单晶X射线结构；通过排除法并得到密度泛函理论计算的支持，推断出45°非对映异构体的存在。对于Mo[TBCFPC]和W[TBCFPC]，两种非对映异构体也通过光谱进行了全面表征，并且它们的1H NMR光谱基本已完全归属。每个非对映异构体都是手性的，并且以两种对映体形式存在（这先前已在一种钨双卟啉的135°形式中得到证明），这确立了金属双卟啉骨架的双重立体异构性质——据我们所知，这是夹心化合物的首次此类证明。
