Organosilicon nitrogen compounds

Cross-Dehydrocoupling of Amines and Silanes Catalyzed by Magnesocenophanes

“…There has been an increasing interest in Si–N compounds in recent years, as their applications in organic chemistry and materials science have made them indispensable compounds. − For instance, polysilazanes are used as precursors in the synthesis of Si–N-based polymers and ceramics and have found applications as ligands in organometallic chemistry. − ,− Due to this versatile use, an easy access to the compounds is of great interest. Established synthesis routes for the formation of Si–N bonds are often complex and produce undesired byproducts. ,− For example, common reaction routes starting from halosilanes and amines , or metal amides , to give monosilazanes, disilylamines, and diaminosilanes also produce coupling products such as hydrogen halides and metal halide salts that have to be separated from the products.…”

“…There has been an increasing interest in Si–N compounds in recent years, as their applications in organic chemistry and materials science have made them indispensable compounds. − For instance, polysilazanes are used as precursors in the synthesis of Si–N-based polymers and ceramics and have found applications as ligands in organometallic chemistry. − ,− Due to this versatile use, an easy access to the compounds is of great interest. Established synthesis routes for the formation of Si–N bonds are often complex and produce undesired byproducts. ,− For example, common reaction routes starting from halosilanes and amines , or metal amides , to give monosilazanes, disilylamines, and diaminosilanes also produce coupling products such as hydrogen halides and metal halide salts that have to be separated from the products. Dehydrocoupling reactions, on the other hand, present a more efficient method for the generation of Si–N bonds that can circumvent these difficulties, as only dihydrogen is produced as a byproduct. , Metal-catalyzed cross-dehydrocoupling reactions of primary or secondary amines with hydridosilanes are therefore of great interest, and many different transition-metal (pre)­catalysts have been developed in the past decade. − With recent developments in s-block catalysis, the advantages of alkaline-earth-metal compounds with regard to the high occurrence in the Earth’s crust of these elements and their low toxicities, in particular magnesium and calcium complexes, in amine–silane cross-dehydrocoupling catalysis has been brought into focus. − Interestingly, only a handful of magnesium complexes have been employed as catalysts in the cross-dehydrocoupling catalysis of amines and silanes (Figure ).…”

“…Established synthesis routes for the formation of Si−N bonds are often complex and produce undesired byproducts. 2,8−10 For example, common reaction routes starting from halosilanes and amines 2,8 or metal amides 9,10 to give monosilazanes, disilylamines, and diaminosilanes also produce coupling products such as hydrogen halides and metal halide salts that have to be separated from the products. Dehydrocoupling reactions, on the other hand, present a more efficient method for the generation of Si−N bonds that can circumvent these difficulties, as only dihydrogen is produced as a byproduct.…”

Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

“…These long-standing synthetic challenges are addressed in catalytic silicon-nitrogen bond formation. The SiÀNb ond is a heavily used moiety across ar ange of fields including applications as bases in organic synthesis, ligandsf or transition-metal and main group compounds, [6] and protecting group agents for alcohols, aldehydes,a nd ketones ( Figure 1A). [7] Similarly,Nsilylationisapowerful protectionm ethod for the functionalization and derivation of biologically important pyrroles and indoles ( Figure 1B).…”

Si–N Heterodehydrocoupling with a Lanthanide Compound

“…30,31 Silamines are also important ligands in coordination chemistry. 32,33 Heterodehydrocoupling is an attractive avenue for silamine preparation versus salt metathesis because the H 2 byproduct is easily separated and simplifies workup. However, selectivity in dehydrocoupling is also challenging as an excess of amine is required.…”