Recent Developments in the Chemistry of Compounds with Silicon–Nitrogen Bonds

Abstract

Introduction Preparation and Properties of the Si  N Bond Aminosilanes Lithium Derivatives of Silylamines Lithium Derivatives of Hydrazines Iminosilanes Cyclic Silicon–Nitrogen Compounds Cyclodisilazanes Cyclotrisilazanes Cyclotetrasilazanes Application of Cyclosilazanes as Precursors for Silicon‐Based Ceramics

N‐Silylation of Amines Mediated by Et3SiH/KOtBu

“…It was found, as expected, that the direct deprotonation of aliphatic amines with KO t Bu is thermodynamically unfavourable [36] (Scheme 2 'Direct Deprotonation' and Table S3). A more accessible energy profile was identified for the reaction of potassium tert-butoxide (8) with trimethylsilane (5) to generate potassium hydride (9). The subsequent deprotonation of the amine substrates 6 with this hydride is highly efficient (Step A in Scheme 2).…”

“…[4][5][6][7] Historical approaches for formation of silazanides, based on condensation between chlorosilanes and amines, present the drawback of generating corrosive HCl as by-product and considerable amounts of salts. [8] In recent years, these methods are complemented by protocols based on a cross-dehydrogenative coupling of hydrosilanes and amines, with H 2 being the exclusive by-product of the catalytic process. In this regard, a comprehensive review of catalytic bond formation reactions for siliconÀ nitrogen (and other heteroatoms) has been published by Kuciński and Hreczycho in 2017.…”

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

“…However, various small molecules and polymers containing the Si−N bond have turned out to be an important class of compounds in both organic and inorganic chemistry; they are also valuable synthetic intermediates. There are several synthetic approaches to obtain these organosilicon derivatives; for example, classical ones are based on the condensation of a halosilane with various amines (aminolysis) or ammonia (ammonolysis) . Unfortunately, these reactions proceed along with the evolution of corrosive byproducts (e.g., HCl, HBr, etc.…”

Introducing the Catalytic Amination of Silanes via Nitrene Insertion

“…Silicon-based compounds bearing Si–N bonds constitute an important class within both organic/inorganic fields with applications ranging from ligands to protecting groups, bases, or functional materials. , Several methods have been reported to date for the construction of Si–N bonds from silanes (Scheme ). In addition to the stoichiometric reaction of chlorosilanes with amines (and subsequent elimination of HCl), the following catalytic processes are known for generating such groups: (a) the dehydrocoupling of amines and hydrosilanes (Scheme , I); (b) the hydrosilylation reaction of hydrolyzable imines (Scheme , II); (c) the hydrosilylation of nitriles (Scheme , III); (d) the use of pyridines as N sources (Scheme , IV); (e) the N-silylation employing vinyl-silanes (Scheme , V) .…”