Franz Roman, Nasemann Sina, Bruhn Clemens, Kelemen Zsolt, Pietschnig Rudolf
Institute for Chemistry and CINSaT, University of Kassel, Heinrich Plett-Strasse 40, 34132, Kassel, Germany.
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics and MTA-BME, Computation Driven Chemistry Research Group, Szent Gellért tér 4, 1111, Budapest, Hungary.
Chemistry. 2021 Jan 7;27(2):641-648. doi: 10.1002/chem.202002481. Epub 2020 Nov 9.
tert-Butyl-substituted diphospha[2]ferrocenophane has been used as a stereochemically confined diphosphane to explore the addition of O, S, Se and Te. Although the diphosphanylchalcogane has been obtained for tellurium, all other chalcogens give diphosphane monochalcogenides. The latter transform via chalcogen-transfer rearrangement to the corresponding diphosphanylchalcoganes upon heating. The kinetics of this rearrangement has been followed with NMR spectroscopy supported by DFT calculations. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry together with DFT studies indicate ferrocene-centred oxidation for most of the compounds presented.
叔丁基取代的二磷杂[2]二茂铁环已被用作立体化学受限的二膦来研究氧、硫、硒和碲的加成反应。尽管已获得碲的二膦基硫属化物，但所有其他硫属元素均生成二膦单硫属化物。后者在加热时通过硫属转移重排转化为相应的二膦基硫属化物。这种重排的动力学通过核磁共振光谱跟踪，并得到密度泛函理论计算的支持。重排过程中的中间体表明硫和硒衍生物的歧化/同歧化机理。循环伏安法与密度泛函理论研究表明，所呈现的大多数化合物以二茂铁为中心发生氧化。
