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Unprecedented Cyclic Isomer of Triazenes: A Computational Identification
Author(s) -
Xin Jingfan,
Ding Yihong
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201700875
Subject(s) - triazene , nitrene , ring (chemistry) , chemistry , nitrogen , structural isomer , stereochemistry , computational chemistry , medicinal chemistry , crystallography , organic chemistry , catalysis
Isomerism is very important in chemistry. Over the past 65 years, the energy‐rich N 3 R 3 family has received considerable attention both experimentally and computationally. Up to now, four isomeric types of N 3 R 3 have been identified, i.e., triazenes I , triimides II , iso‐triazenes III , and cyclo‐triazanes IV . In this work, via the composite CBS‐QB3 study on the isomers and transition states of N 3 H 3 —the simplest N 3 R 3 system, we unexpectedly found a new structural type V , which contains a N 3 three‐membered ring with one nitrogen‐nitrogen dative bond in the ring (i.e., cyclic ammonia‐nitrene interaction). Of all the N 3 H 3 isomers, V lies the highest in energy (78.7 kcal/mol above the global triazene) and possesses a relatively low conversion barrier 8.9 kcal/mol. Yet quite promisingly, suitably choosing substituents can tune the rate‐determining barrier of V to reach around 20 kcal/mol. Thus, synthesis of the newly found triazene isomer V is highly probable.