Ullrich Sebastian, Kovačević Borislav, Koch Björn, Harms Klaus, Sundermeyer Jörg
Fachbereich Chemie , Philipps-University Marburg , Hans-Meerwein-Straße , 35032 Marburg , Germany . Email:
The Group for Computational Life Sciences , Rudjer Bošković Institute , Bijenička c. 54 , HR-10000 Zagreb , Croatia.
Chem Sci. 2019 Aug 16;10(41):9483-9492. doi: 10.1039/c9sc03565f. eCollection 2019 Nov 7.
A new generation of carbodiphosphoranes (CDPs), incorporating pyrrolidine, tetramethylguanidine, or tris(dimethylamino)phosphazene as substituents is introduced as the most powerful class of non-ionic carbon superbases on the basicity scale to date. The synthetic approach as well as NMR spectroscopic and structural characteristics in the free and protonated form are described. Investigation of basicity in solution and in the gas phase by experimental and theoretical means provides the to our knowledge first reported p values for CDPs in the literature and suggest them as upper tier superbases.
引入了新一代碳二磷烯（CDP），其包含吡咯烷、四甲基胍或三（二甲氨基）磷腈作为取代基，是迄今为止碱性标度上最强大的一类非离子型碳超碱。描述了其合成方法以及游离形式和质子化形式的核磁共振光谱和结构特征。通过实验和理论手段对溶液和气相中的碱性进行研究，提供了据我们所知文献中首次报道的CDP的pKa值，并表明它们是顶级超碱。
