期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 45, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211450
关键词
Copper; Density Functional Calculations; Nitrogen Oxides; Reaction Mechanisms; Substituent Effects
资金
- NIH [GM085774]
This study reveals the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction through quantum chemical research on Cu cyclams. The results indicate that steric effect is the primary factor, and electronic factor is the secondary factor, but the combined effects can lead to unexpected reactions.
HNO has broad chemical and biomedical properties. Metal complexes and derivatives are widely used to make excellent HNO sensors. However, their favorable mechanistic origins are largely unknown. Cu cyclam is a useful platform to make excellent HNO sensors including imaging agents. A quantum chemical study of Cu cyclams with various substitutions was performed, which reproduced diverse experimental reactivities. Structural, electronic, and energetic profiles along reaction pathways show the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction. Results reveal that steric effect is primary and electronic factor is secondary (if the redox potential is sufficient), but their interwoven effects can lead to unexpected reactivity, which looks mysterious experimentally but can be explained computationally. This work suggests rational substituent design ideas and recommends a theoretical study of a new design to save time and cost due to its subtle effect.
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