Rigo Massimo, Habraken Evi R M, Bhattacharyya Koyel, Weber Manuela, Ehlers Andreas W, Mézailles Nicolas, Slootweg J Chris, Müller Christian
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstrasse 34-36, 14195, Berlin, Germany.
Van't Hoff Institute of Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1090 GD, Amsterdam, The Netherlands.
Chemistry. 2019 Jul 2;25(37):8769-8779. doi: 10.1002/chem.201900938. Epub 2019 May 21.
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%V ) was calculated to get insight into the steric properties, [LNi(CO) ] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L-M interaction. Au coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of P compounds were successfully used in the Au -catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts.
合成了一系列取代磷杂苯、1-磷杂桶烯和5-磷杂半环戊二烯，并对其作为均相催化反应配体的潜在应用进行了评估。通过计算它们的埋藏体积（%V）来深入了解其空间性质，制备了[LNi(CO)]配合物以确定相应的托尔曼电子参数。对[LAuCl]配合物进行的ETS-NOCV（扩展过渡态化学价自然轨道）计算进一步估算了L-M相互作用中σ和π的贡献。制备了所选实例的金配位化合物，并通过单晶X射线衍射进行了表征。最后，这三类磷化合物成功用于N-2-丙炔-1-基苯甲酰胺的金催化环异构化反应，显示出非常好的活性和选择性，与报道的阳离子磷基金催化剂的数据相当。
