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Stable, but still reactive – investigations on the effects of Lewis acid binding on copper nitrene intermediates
Author(s) -
Warm Katrin,
Monte Pérez Inés,
Kuhlmann Uwe,
Hildebrandt Peter,
Farquhar Erik,
Swart Marcel,
Ray Kallol
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100092
Subject(s) - nitrene , copper , amination , chemistry , reactive intermediate , redox , substituent , lewis acids and bases , photochemistry , radical , computational chemistry , combinatorial chemistry , stereochemistry , organic chemistry , catalysis
Copper nitrenes are proposed as reactive intermediates in a number of copper mediated aziridination and amination reactions. However, the isolation and characterization of such intermediates have proved challenging because of their transient nature. One successful approach for the stabilization of the copper‐nitrene cores is the employment of a redox innocent Lewis acid (LA) like Sc 3+ . We herein report the stabilization of two transient copper nitrene species 3 and 4 in the absence of LAs by employing electronegative −CF 3 and −NO 2 groups in the nitrene substituent. Detailed investigations of the spectroscopic properties of 3 and 4 by theoretical and experimental methods, and a comparison of their reactivities in presence and absence of LAs provide some vital insights into the effect of LAs on the geometric and electronic structures of the copper nitrenes.