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Abstract
The behavior of the Lewis-acid adducts of two copper-nitrene [Cu(NR)](+) complexes in nitrene-transfer and H-atom abstraction reactions have been demonstrated to depend on the nature of the nitrene substituents. Two-state reactivity, in which a singlet ground state and a nearby triplet excited-state both contribute, provides a useful model for interpreting reactivity trends of the two compounds.
Highlights
The behavior of the Lewis-acid adducts of two copper–nitrene [Cu(NR)]+ complexes in nitrene-transfer and H-atom abstraction reactions have been demonstrated to depend on the nature of the nitrene substituents
While concerted aziridination reactions have been proposed to be favored on the closed-shell [CuIII(NR)]+ singlet surface,[8] amination reactions were suggested to proceed via a stepwise H-atom abstraction/radical rebound (HAT/RR) pathway on the [CuII(NR)]+ triplet surface.[1]
Our group reported the spectroscopic characterization of a Lewis-acid adduct of a cationic copper-tosylnitrene [CuII-(NTs)Sc(OTf)3] species (1; Ts = tosyl; Scheme 1), the electronic structure of which could be best described in terms of a Cu(II) ion antiferromagnetically coupled to a nitrene radical thereby stabilizing an open-shell singlet ground state.[11]
Summary
The behavior of the Lewis-acid adducts of two copper–nitrene [Cu(NR)]+ complexes in nitrene-transfer and H-atom abstraction reactions have been demonstrated to depend on the nature of the nitrene substituents. Our group reported the spectroscopic characterization of a Lewis-acid adduct of a cationic copper-tosylnitrene [CuII-(NTs)Sc(OTf)3] species (1; Ts = tosyl; Scheme 1), the electronic structure of which could be best described in terms of a Cu(II) ion antiferromagnetically coupled to a nitrene radical thereby stabilizing an open-shell singlet ground state.[11] Reactivity studies revealed that this species aminates sp[3] C–H bonds in substrates such as toluene and even cyclohexane in modest yields (21–35%).
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