Rational design of an argon-binding superelectrophilic anion
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- Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, 04103 Leipzig, Germany,
- Anorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, 42119 Wuppertal, Germany,
- Institut für Angewandte und Physikalische Chemie, Fachbereich 2-Biologie/Chemie, Universität Bremen, 28359 Bremen, Germany,
- Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352,
- Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352,
- Department of Chemistry, University of the Free State, 9300 Bloemfontein, South Africa,
- Institut für Anorganische Chemie und Kristallographie, Fachbereich 2-Biologie/Chemie, Universität Bremen, 28359 Bremen, Germany,
- Advanced Computing, Mathematics and Data Division, Pacific Northwest National Laboratory, Richland, WA 99352,, Department of Chemistry, University of Washington, Seattle, WA 98195,
- Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352,, Department of Chemistry, Purdue University, West Lafayette, IN 47907
Chemically binding to 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 are composed of a strong electrophilic center firmly embedded in a negatively charged 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. As a result, the detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts another chapter in the metal-free activation of particularly inert compounds and elements.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- Grant/Contract Number:
- AC02-05CH11231
- OSTI ID:
- 1505256
- Alternate ID(s):
- OSTI ID: 1528932
- Journal Information:
- Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 116 Journal Issue: 17; ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of SciencesCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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