Rational design of an argon-binding superelectrophilic anion

被引：73

作者：

Mayer, Martin ^{[1
]}

van Lessen, Valentin ^{[2
]}

Rohdenburg, Markus ^{[3
]}

Hou, Gao-Lei ^{[4
]}

Yang, Zheng ^{[4
]}

Exner, Rudiger M. ^{[2
]}

Apra, Edoardo ^{[5
]}

Azov, Vladimir A. ^{[6
]}

Grabowsky, Simon ^{[7
]}

Xantheas, Sotiris S. ^{[8
,9
]}

Asmis, Knut R. ^{[1
]}

Wang, Xue-Bin ^{[4
]}

Jenne, Carsten ^{[2
]}

Warneke, Jonas ^{[4
,10
]}

机构：

[1] Univ Leipzig, Wilhelm Ostwald Inst Phys & Theoret Chem, D-04103 Leipzig, Germany

[2] Berg Univ Wuppertal, Anorgan Chem, Fak Math & Nat Wissensch, D-42119 Wuppertal, Germany

[3] Univ Bremen, Fachbereich 2 Biol Chem, Inst Angew & Phys Chem, D-28359 Bremen, Germany

[4] Pacific Northwest Natl Lab, Phys Sci Div, Richland, WA 99352 USA

[5] Pacific Northwest Natl Lab, Environm Mol Sci Lab, Richland, WA 99352 USA

[6] Univ Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa

[7] Univ Bremen, Fachbereich Biol Chem 2, Inst Anorgan Chem & Kristallog, D-28359 Bremen, Germany

[8] Pacific Northwest Natl Lab, Adv Comp Math & Data Div, Richland, WA 99352 USA

[9] Univ Washington, Dept Chem, Seattle, WA 98195 USA

[10] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2019年 / 116卷 / 17期

关键词：

superelectrophilic anions; multiple-charged anions; Ar compounds; photoelectron spectroscopy; dodecaborates; MULTIPLY-CHARGED ANIONS; VIBRATIONAL SPECTROSCOPY; ELECTRON-AFFINITY; GAS; STABILITY; CHEMISTRY; HARF; TRANSITION; GENERATION; CLUSTERS;

D O I：

10.1073/pnas.1820812116

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

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 [B-12(CN)(12)](2-) the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B-12(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.

引用

页码：8167 / 8172

页数：6

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