A Nucleophilicity Scale for the Reactivity of Diazaphospholenium Hydrides: Structural Insights and Synthetic Applications

Angewandte Chemie
Jingjing ZhangJin-Pei Cheng

Abstract

Nucleophilicity parameters (N, sN ) of a group of representative diazaphospholenium hydrides were derived by kinetic investigations of their hydride transfer to a series of reference electrophiles with known electrophilicity (E) values, using the Mayr equation log k2 =sN (N+E). The N scale covers over ten N units, ranging from the most reactive hydride donor (N=25.5) to the least of the scale (N=13.5). This discloses the highest N value ever quantified in terms of Mayr's nucleophilicity scales reported for neutral transition-metal-free hydride donors and implies an exceptional reactivity of this reagent. Even the least reactive hydride donor of this series is still a better hydride donor than those of many other nucleophiles such as the C-H, B-H, Si-H and transition-metal M-H hydride donors. Structure-reactivity analysis reveals that the outstanding hydricity of 2-H-1,3,2-diazaphospholene benefits from the unsaturated skeleton.

References

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Feb 2, 2017·Angewandte Chemie·Matt R AdamsAlexander W H Speed
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Jun 12, 2018·The Journal of Physical Chemistry. B·Jin-Dong YangXiao-Qing Zhu

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Citations

May 3, 2019·Angewandte Chemie·John H ReedNicolai Cramer
Mar 12, 2020·Chemical Communications : Chem Comm·Travis LundriganAlexander W H Speed
May 27, 2020·Chemistry : a European Journal·Darren M C Ould, Rebecca L Melen
Nov 7, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Darren M C OuldRebecca L Melen
Oct 21, 2020·Chemical Society Reviews·Alexander W H Speed
Feb 4, 2021·The Journal of Organic Chemistry·Manuel OrlandiGiulia Licini
Aug 24, 2019·Journal of the American Chemical Society·Travis LundriganAlexander W H Speed

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