TY - JOUR
T1 - Hydrogen-Bonded Complexes of Methylnitrene
AU - Du, Yanqi
AU - Li, Xiaolong
AU - Jiang, Junjie
AU - Fan, Wenbin
AU - Mu, Di
AU - Li, Quansong
AU - Ma, Ruitao
AU - Yu, Qi
AU - Zeng, Xiaoqing
N1 - Publisher Copyright:
© 2025 American Chemical Society.
PY - 2025
Y1 - 2025
N2 - Understanding the microsolvation effects of nitrenes is of vital importance in applied nitrene chemistry. Herein, we report the structures and reactivity of the prototype microsolvated systems consisting of the simplest alkylnitrene CH3N and hydrogen bond donors HX (X = OH, Cl). Specifically, the 1:1 complexes of triplet CH3N with H2O and HCl were generated from photolysis of the corresponding amine precursors CH3NHX in solid Ar-matrices at 6 K. Characterization of the two complexes CH3N···HX with matrix-isolation IR and UV-vis spectroscopy is supported by D-isotope labeling experiments and quantum chemical calculations, and the results confirm that the electron-deficient nitrene center acts as hydrogen bond acceptor. Consistent with the observed absorptions at around 310 nm for the hydrogen-bonded nitrene, photoexcitation of CH3N···HX at 310 nm promotes competing rearrangement of the nitrene to imine via 1,2-H migration and H-X bond insertion reactions, for which the underlying mechanism has been revealed by the CASPT2//CASSCF calculations.
AB - Understanding the microsolvation effects of nitrenes is of vital importance in applied nitrene chemistry. Herein, we report the structures and reactivity of the prototype microsolvated systems consisting of the simplest alkylnitrene CH3N and hydrogen bond donors HX (X = OH, Cl). Specifically, the 1:1 complexes of triplet CH3N with H2O and HCl were generated from photolysis of the corresponding amine precursors CH3NHX in solid Ar-matrices at 6 K. Characterization of the two complexes CH3N···HX with matrix-isolation IR and UV-vis spectroscopy is supported by D-isotope labeling experiments and quantum chemical calculations, and the results confirm that the electron-deficient nitrene center acts as hydrogen bond acceptor. Consistent with the observed absorptions at around 310 nm for the hydrogen-bonded nitrene, photoexcitation of CH3N···HX at 310 nm promotes competing rearrangement of the nitrene to imine via 1,2-H migration and H-X bond insertion reactions, for which the underlying mechanism has been revealed by the CASPT2//CASSCF calculations.
UR - http://www.scopus.com/pages/publications/105009693005
U2 - 10.1021/acs.jpclett.5c01270
DO - 10.1021/acs.jpclett.5c01270
M3 - Article
C2 - 40609010
AN - SCOPUS:105009693005
SN - 1948-7185
SP - 7127
EP - 7133
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
ER -