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A Nucleophilicity Scale for the Reactivity of Diazaphospholenium Hydrides: Structural Insights and Synthetic Applications
Author(s) -
Zhang Jingjing,
Yang JinDong,
Cheng JinPei
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901456
Subject(s) - nucleophile , hydride , electrophile , reactivity (psychology) , chemistry , reagent , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , metal , catalysis , medicine , alternative medicine , pathology
Nucleophilicity parameters ( N , s N ) 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 k 2 = s N ( 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.