English

The title of the article is called “The Chemistry of Trichlorosilane - Tertiary Amine Combinations”. The author is called Robert A. Benkeser. The information concerns the mechanisms of chemical reactions involving trichlorosilane – tertiary amine combinations and feasibility of the existence of SiCl3- anion. The problem of the experimental verification of the concept of SiCl3- anion is concerned here. The problem of the mechanism of the trichlorosilane dismutation induced by tertiary and quaternary amines I’m studying now bears on the mechanism of the interaction between trichlorosilane, dichlorosilane, and monochlorosilane molecules and amine molecule. Such complex systems are very difficult to study and the key to understanding their behavior is to investigate these systems step by step.

Our knowledge about the nature of the interaction between trichlorosilane and amines hasn’t changed a lot since the pioneer works by Benkeser published in 1970’s. So it’s crucial to study them. In this paper, the author used different methods to explore the chemistry of trichlorosilane – tertiary amine combinations. While the concept of SiCl3- anion was postulated earlier, the nuclear magnetic resonance and hydrogen–deuterium exchange data obtained by the author constitute the first experimental evidence for its existence. The author examined reaction between trichlorosilane and different phenylacetylenes catalyzed by tertiary amines. He noted that the presence of polar solvent is essential for the reaction to proceed at any appreciable rate and electron-withdrawing substituents on the phenyl ring causes a more rapid rate of the addition. The study of the reactions between trichlorosilane – tertiary amine combinations and organic halides allowed the author to propose a mechanism of the nucleophilic displacement by SiCl3- anion on halogen. Several addition experiments were carried out to exclude probable reaction pathways that include silylenes or carbenes as intermediates and the results of these experiments were entirely negative. The research of the reactions between trichlorosilane – tertiary amine combinations and substituted benzylic halides and 1,1,1-trichloro-2-propanone allowed the author to assume that trichlorosilyl anion has the potential of attacking not only on halogen but also on carbon and oxygen.

The chief aim of the present paper is to shed light on the chemistry of the interaction between trichlorosilane and tertiary amines. The experimental data obtained by the author allows concluding that thrichlorosilyl anion is likely to exist as a reaction intermediate. The research allows to predict the outcome of reactions that involve trichlorosilane – tertiary amine combinations.