Naslov
A Phosphorus Bisylide : Exploring a New Class of Superbases with Two Interacting Carbon Atoms as Basicity Centers

Autori
Kogel, Julius, F. ; Margetić, Davor ; Xie, Xiulan ; Finger, Lars, H. ; Sundermeyer, Jorg

Izvornik
Angewandte Chemie. International edition (1433-7851) 56 (2017), 11; 3090-3093

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
phosphorus ylides, superbase, synthesis

Sažetak
Herein we present the first superbase MHPN with two interacting P-ylide entities. Unlike classical proton sponges, this novel compound class has carbon atoms as basicity centers which are forced into close proximity by a naphthalene scaffold. The bisylide exhibits an experimental pKBH+ value of 33.3±0.2 on the MeCN scale and a calculated gas-phase proton affinity of 277.9 kcal/mol−1 M062X/6-311+G**//M062X/6-31G*+ZPVE method) exceeding that of the corresponding monoylide by nearly 15 kcal/mol. The origin of the unexpectedly high basicity of the new bisylide was investigated by NMR spectroscopic methods, single-crystal Xray diffraction as well as theoretical calculations and can be partly attributed to the rapid exchange of the “acidic” proton between the two basic carbon atoms after protonation.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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