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Nitrogen‐Based Lewis Acids: Synthesis and Reactivity of a Cyclic (Alkyl)(Amino)Nitrenium Cation
Author(s) -
Zhou Jiliang,
Liu Liu Leo,
Cao Levy L.,
Stephan Douglas W.
Publication year - 2018
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.201713118
Subject(s) - chemistry , electrophile , lewis acids and bases , cationic polymerization , reactivity (psychology) , alkyl , homo/lumo , medicinal chemistry , adduct , nitrogen , nitrogen atom , stereochemistry , organic chemistry , molecule , catalysis , medicine , alternative medicine , pathology
A room‐temperature‐stable crystalline cyclic (alkyl)(amino)nitrenium cation 2 features cationic nitrogen atom with a smaller HOMO–LUMO gap compared to that of a 1,2,3‐triazolium 5 (an N‐heterocyclic nitrenium cation). The low‐lying LUMO of 2 results in an enhanced electrophilicity, which allowed for the formation of Lewis adducts with neutral Lewis bases, such as Me 3 P, n Bu 3 P, and I i Pr. The N‐based Lewis acid 2 also forms an FLP with t Bu 3 P but subsequently reacts with (PrS) 2 to cleave the S−S bond. Both experimental and theoretical results suggest that the Lewis acidity of 2 is stronger than its N 3 analogues.