Makale detayı · 2020
Heavy-Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2-Formylarylnitrene to a Singlet 2,1-Benzisoxazole
Dergi
ANGEWANDTE CHEMIE-INTERNATIONAL EDITIONISSN 1433-7851
ISSN kaydı başka bir dergiye işaret ediyor; ad YÖKSİS kaydından.
- Yıl
- 2020
- Tür
- article
Veri kaynağı ayrımı
- YÖKSİS YÖKSİS makale kaydı
- YÖKSİS dergi adı ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
- Katalog eşleşmesi (ISSN) Angewandte Chemie - International Edition
- OpenAlex OpenAlex zenginleştirmesi (özet, atıf, konular)
Özet
OpenAlex · İngilizce
Abstract Not long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy‐atom QMT reaction. Triplet syn‐2‐formyl‐3‐fluorophenylnitrene, generated in argon matrices by UV‐irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4‐fluoro‐2,1‐benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature‐independent rate constants (k≈1.4×10−3 s−1; half‐life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy‐atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy‐atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.
Konular
Atıflar
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38 atıf
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Yerel katalogda bu makaleye atıf yapan 8 yayın (OpenAlex referans eşleşmesi; tam dünya listesi değildir).
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