Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125, Saarbrücken, Germany.
Department of Chemistry, Faculty of Science and Letters, Aksaray University, 68100, Aksaray, Turkey.
Angew Chem Int Ed Engl. 2016 Aug 26;55(36):10913-7. doi: 10.1002/anie.201605699. Epub 2016 Aug 11.
The reaction of MesLi (Mes=2,4,6-trimethylphenyl) with the electrophilic phosphasilene R2 (NMe2 )Si-RSi=PNMe2 (2, R=Tip=2,4,6-triisopropylphenyl) cleanly affords R2 (NMe2 )Si-RSi=PMes and thus provides the first example of a substitution reaction at an unperturbed Si=P bond. In toluene, the reaction of 2 with lithium disilenide, R2 Si=Si(R)Li (1), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo[1.1.0]butane analogue as the final product, which was further characterized as its Fe(CO)4 complex. In contrast, in 1,2-dimethoxyethane the reaction of 1 with 2 results in an unprecedented metal-amino exchange reaction.
MesLi（Mes=2,4,6-三甲基苯基）与亲电膦硅烯 R2（NMe2）Si-RSi=PNMe2（2，R=Tip=2,4,6-三异丙基苯基）反应，可得到 R2（NMe2）Si-RSi=PMes，从而提供了首例在未受干扰的 Si=P 键上进行取代反应的例子。在甲苯中，2 与二硅化锂 R2 Si=Si（R）Li（1）的反应显然也经过了初始的亲核取代步骤（正如 DFT 计算所表明的），但得到的是最终产物饱和双环[1.1.0]丁烷类似物，其进一步被表征为其 Fe(CO)4 配合物。相比之下，在 1,2-二甲氧基乙烷中，1 与 2 的反应导致了前所未有的金属-氨基交换反应。
