Wagner Hannah K, Wadepohl Hubert, Ballmann Joachim
Anorganisch-Chemisches Institut, Universität Heidelberg Im Neuenheimer Feld 276 D-69120 Heidelberg Germany
Chem Sci. 2021 Jan 29;12(10):3693-3701. doi: 10.1039/d0sc06128j.
A metal-templated synthetic route to cyclic (aryl)(ylidic) mesoionic carbenes (s) featuring an endocyclic P-ylide is presented. This approach, which requires metal templates with two -positioned open coordination sites, is based on the controlled cyclisation of a ,'-diisopropyl-substituted 2,2'-diphosphinotolane () and leads to chelate complexes coordinated by a phosphine donor and the carbon atom. The C-P bond formation involved in the former partial cyclisation of proceeds under mild conditions and was shown to be applicable all over the d-block. In the presence of a third -positioned open coordination site, the P-C bond formation was found to be reversible, as shown for a series of molybdenum complexes. DFT modelling studies are in line with an interpretation of the target compounds as s.
本文介绍了一种以金属为模板的合成路线，用于制备具有环内磷叶立德的环状（芳基）（叶立德）中氮茚型卡宾。这种方法需要具有两个定位开放配位位点的金属模板，它基于α,α'-二异丙基取代的2,2'-二膦基甲苯（ ）的可控环化反应，并生成由膦供体和碳原子配位的螯合配合物。前者在温和条件下进行的部分环化反应中涉及的C-P键形成反应已被证明适用于整个d区。如一系列钼配合物所示，在存在第三个定位开放配位位点的情况下，发现P-C键的形成是可逆的。密度泛函理论（DFT）建模研究与将目标化合物解释为中氮茚型卡宾的观点一致。
