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Unusual Nitrene Oxidation Product Formation by Metathesis Involving the Dioxygen O−O and Borylnitrene B−N Bonds
- Source :
- Chemistry (Weinheim an Der Bergstrasse, Germany)
- Publication Year :
- 2020
- Publisher :
- Wiley, 2020.
-
Abstract
- The reaction of dioxygen with nitrenes can have significant energy barriers, although both reactants are triplet diradicals and the formation of nitroso‐O‐oxides is spin‐allowed. By means of matrix‐isolation infrared spectroscopy in solid argon, nitrogen, and neon, and through high‐level computational quantum chemistry, it is shown herein that a 3‐nitreno‐1,3,2‐benzodioxaborole CatBN (Cat=catecholato) reacts with dioxygen under cryogenic conditions thermally at temperatures as low as 7 K to produce two distinct products, an anti‐nitroso‐O‐oxide and a nitritoborane CatBONO. The computed barriers for the formation of nitroso‐O‐oxide isomers are very low. Whereas anti‐nitroso‐O‐oxide is kinetically trapped, its bisected isomer has a very low barrier for metathesis, yielding the CatBO+NO radicals in a strongly exothermic reaction; these radicals can combine under matrix‐isolation conditions to give nitritoborane CatBONO. The trapped isomer, anti‐nitroso‐O‐oxide, can form the nitritoborane CatBONO only after photoexcitation, possibly involving isomerization to the bisected isomer of anti‐nitroso‐O‐oxide.<br />Overcoming barriers: The reaction of dioxygen with nitrenes can have significant energy barriers. The reaction mechanism of borylnitrene 1 is investigated through matrix‐isolation infrared spectroscopy and high‐level computational quantum chemistry. Borylnitrene 1 reacts with dioxygen to form nitritoborane 3 a via nitroso‐O‐oxide isomer 2 c. Nitroso‐O‐oxide isomer 2 a is stable towards thermal reaction to 3 a, but dyotropic rearrangement can be achieved photochemically.
- Subjects :
- Exothermic reaction
Reaction mechanism
Full Paper
010405 organic chemistry
Chemistry
Nitrene
Radical
Organic Chemistry
Infrared spectroscopy
General Chemistry
Full Papers
radicals
010402 general chemistry
Photochemistry
Metathesis
01 natural sciences
Quantum chemistry
Catalysis
0104 chemical sciences
nitrenes
density functional calculations
Reaction Mechanisms
boron
Isomerization
Subjects
Details
- ISSN :
- 15213765 and 09476539
- Volume :
- 26
- Database :
- OpenAIRE
- Journal :
- Chemistry – A European Journal
- Accession number :
- edsair.doi.dedup.....88daebac5f76af02541509bf0408646e