Strain‐Modulated Reactivity: An Acidic Silane

نویسندگان

چکیده

Compounds of main-group elements such as silicon are attractive candidates for green and inexpensive catalysts. For them to compete with state-of-the-art transition-metal complexes, new reactivity modes must be unlocked controlled, which can achieved through strain. Using a tris(2-skatyl)methylphosphonium ([TSMPH3]+) scaffold, we prepared the strained cationic silane [TSMPSiH]+. In stark contrast generally hydridic Si−H bond character, it is acidic an experimental pKaDMSO within 4.7–8.1, lower than in phenol, benzoic acid, few hydrosilanes reported pKa values. We show that ring strain significantly contributes this unusual acidity along inductive electrostatic effects. The conjugate base, TSMPSi, activates THF molecule presence CH-acids generate highly fluxional alkoxysilane via trace amounts [TSMPSiH]+ functioning strain-release Lewis acid. This reaction involves formal oxidation-state change from SiII SiIV, presenting intriguing similarities transition-metal-mediated processes.

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ژورنال

عنوان ژورنال: Angewandte Chemie

سال: 2021

ISSN: ['1521-3773', '1433-7851', '0570-0833']

DOI: https://doi.org/10.1002/ange.202015960