Rational design of an argon-binding superelectrophilic anion

Mayer, Martin; van Lessen, Valentin; Rohdenburg, Markus; Hou, Gao-Lei; Yang, Zheng; Exner, Rüdiger M.; Aprà, Edoardo; Azov, Vladimir A.; Grabowsky, Simon; Xantheas, Sotiris S.; Asmis, Knut R.; Wang, Xue-Bin; Jenne, Carsten; Warneke, Jonas (2019). Rational design of an argon-binding superelectrophilic anion. Proceedings of the National Academy of Sciences of the United States of America - PNAS, 116(17), pp. 8167-8172. National Academy of Sciences NAS 10.1073/pnas.1820812116

[img] Text
060_Mayer2019_PNAS.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (1MB) | Request a copy

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. 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.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Grabowsky, Simon

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0027-8424

Publisher:

National Academy of Sciences NAS

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

20 Jan 2020 11:01

Last Modified:

20 Jan 2020 11:01

Publisher DOI:

10.1073/pnas.1820812116

BORIS DOI:

10.7892/boris.138392

URI:

https://boris.unibe.ch/id/eprint/138392

Actions (login required)

Edit item Edit item
Provide Feedback