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- Title
A Phosphorus Bisylide: Exploring a New Class of Superbases with Two Interacting Carbon Atoms as Basicity Centers.
- Authors
Kögel, Julius F.; Margetić, Davor; Xie, Xiulan; Finger, Lars H.; Sundermeyer, Jörg
- Abstract
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 p KBH+ 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−1. The origin of the unexpectedly high basicity of the new bisylide was investigated by NMR spectroscopic methods, single-crystal X-ray 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.
- Subjects
PHOSPHORUS compounds; YLIDES; SUPERBASES (Chemistry); BASICITY; NAPHTHALENE; PHOSPHAZENES; PROTON affinity; NUCLEAR magnetic resonance spectroscopy
- Publication
Angewandte Chemie International Edition, 2017, Vol 56, Issue 11, p3090
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201612446