Rational design of an argon-binding superelectrophilic anion
Abstract
Chemically binding argon (Ar) at room temperature has remained the privilege of the most reactive electrophiles, all of which are cationic (or even dicationic) in nature. Herein, we report a concept for the rational design of anionic superelectrophiles that comprise a strong electrophilic center firmly embedded in a negativelycharged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B12(CN)12]2-, the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B12(CN)11]-, which indeed spontaneously binds Ar at 298 K. Our mass spectrometric and spectroscopic studies are accompanied by high-level computational investigations including a bonding analysis of the exceptional B-Ar bond. The first detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts a new chapter in the metal-free activation of particularly inert compounds and elements.
- Authors:
-
- Universitat Leipzig
- Bergische Universitat Wuppertal
- Universitat Bremen
- UNIVERSITY PROGRAMS
- BATTELLE (PACIFIC NW LAB)
- Universiteit van die Vrystaat
- International University Bremen
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1530557
- Report Number(s):
- PNNL-SA-140803
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 116; Journal Issue: 17
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Mayer, Martin, Van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rudiger M., Apra, Edoardo, Azov, Vladimir A., Grabowsky, SImon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, and Warneke, Jonas. Rational design of an argon-binding superelectrophilic anion. United States: N. p., 2019.
Web. doi:10.1073/pnas.1820812116.
Mayer, Martin, Van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rudiger M., Apra, Edoardo, Azov, Vladimir A., Grabowsky, SImon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, & Warneke, Jonas. Rational design of an argon-binding superelectrophilic anion. United States. https://doi.org/10.1073/pnas.1820812116
Mayer, Martin, Van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rudiger M., Apra, Edoardo, Azov, Vladimir A., Grabowsky, SImon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, and Warneke, Jonas. 2019.
"Rational design of an argon-binding superelectrophilic anion". United States. https://doi.org/10.1073/pnas.1820812116.
@article{osti_1530557,
title = {Rational design of an argon-binding superelectrophilic anion},
author = {Mayer, Martin and Van Lessen, Valentin and Rohdenburg, Markus and Hou, Gao-Lei and Yang, Zheng and Exner, Rudiger M. and Apra, Edoardo and Azov, Vladimir A. and Grabowsky, SImon and Xantheas, Sotiris S. and Asmis, Knut R. and Wang, Xue-Bin and Jenne, Carsten and Warneke, Jonas},
abstractNote = {Chemically binding argon (Ar) at room temperature has remained the privilege of the most reactive electrophiles, all of which are cationic (or even dicationic) in nature. Herein, we report a concept for the rational design of anionic superelectrophiles that comprise a strong electrophilic center firmly embedded in a negativelycharged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B12(CN)12]2-, the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B12(CN)11]-, which indeed spontaneously binds Ar at 298 K. Our mass spectrometric and spectroscopic studies are accompanied by high-level computational investigations including a bonding analysis of the exceptional B-Ar bond. The first detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts a new chapter in the metal-free activation of particularly inert compounds and elements.},
doi = {10.1073/pnas.1820812116},
url = {https://www.osti.gov/biblio/1530557},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 17,
volume = 116,
place = {United States},
year = {Tue Apr 23 00:00:00 EDT 2019},
month = {Tue Apr 23 00:00:00 EDT 2019}
}
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