“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐<i>closo</i>‐dodecaborate

Während Reaktionen zwischen Ionen und neutralen Molekülen in der Gasphase umfangreich untersucht wurden, sind Reaktionen zwischen molekularen Ionen gleicher Polarität weitestgehend unerforscht. Wir zeigen, dass Reaktionen zwischen in der Gasphase erzeugten Fragmentionen und molekularen Ionen derselben Polarität durch Abscheiden beider Reagenzien auf einer Oberfläche mittels Ion Soft-Landing mçglich sind. Reaktive [B 12 I 11 ] 1À -Anionen wurden auf einer Oberfläche gelandet, auf welcher zuvor, normalerweise unreaktive, [B 12 I 12 ] 2À -Anionen deponiert wurden. Die Ex-situ-Analyse des gebildeten Materials zeigt, dass [B 24 I 23 ] 3À -Ionen gebildet wurden. DFT-Rechnungen zeigen, dass das Produkt in der Gasphase metastabil ist. Die ladungsbalancierte Umgebung einer geerdeten Oberfläche kann jedoch das dreifach geladene Produkt stabilisieren, wie Modellrechnungen bestätigen. Dies erçffnet neue Mçglichkeiten für die Erzeugung von hochgeladenen Clustern unter Verwendung unkonventioneller Molekülbausteine aus der Gasphase.

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Anionen‐Anionen‐Chemie mit massenselektierten Fragmentionen auf Oberflächen

Yang

Behrend

Knorke

et al. 2021

Angewandte Chemie

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Anion–Anion Chemistry with Mass‐Selected Molecular Fragments on Surfaces

et al. 2021

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While reactions between ions and neutral molecules in the gas phase have been studied extensively, reactions between molecular ions of same polarity remain relatively unexplored. Herein we show that reactions between fragment ions generated in the gas phase and molecular ions of the same polarity are possible by soft‐landing of both reagents on surfaces. The reactive [B 12 I 11 ] 1− anion was deposited on a surface layer built up by landing the generally unreactive [B 12 I 12 ] 2− . Ex‐situ analysis of the generated material shows that [B 24 I 23 ] 3− was formed. A computational study shows that the product is metastable in the gas phase, but a charge‐balanced environment of a grounded surface may stabilize the triply charged product, as suggested by model calculations. This opens new opportunities for the generation of highly charged clusters using unconventional building blocks from the gas phase.

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One‐pot Annulation for Biaryl‐fused Monocarba‐closo‐dodecaborate through Aromatic B−H Bond Disconnection

Akimoto

Otsuka

Miyamoto

et al. 2018

Chemistry An Asian Journal

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We have developed a one-pot annulation reaction of monocarba-closo-dodecaborate with cyclic diaryliodonium salts to afford biaryl-fused derivatives. Aryl functionalities are introduced at both the 1-carbon and unreactive ortho-boron vertices of the "σ-aromatic" carborane cage without the need for pre-functionalization. DFT calculations revealed that the palladium-catalyzed C-B bond-formation step in this process proceeds through a concerted metalation-deprotonation (CMD)-type pathway for the B-H bond disconnection on the aromatic cage, though such bonds are generally regarded as hydridic.

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“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

Cited by 8 publications

References 41 publications

Anionen‐Anionen‐Chemie mit massenselektierten Fragmentionen auf Oberflächen

Anionen‐Anionen‐Chemie mit massenselektierten Fragmentionen auf Oberflächen

Anion–Anion Chemistry with Mass‐Selected Molecular Fragments on Surfaces

One‐pot Annulation for Biaryl‐fused Monocarba‐closo‐dodecaborate through Aromatic B−H Bond Disconnection

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