Sustainable preparation of aminosilane monomers, oligomers, and polymers through Si–N dehydrocoupling catalysis

Abstract

This article covers historical and recent efforts to catalyze the dehydrocoupling of amines and silanes, a direct method for Si‒N bond formation that offers hydrogen as a byproduct. In some...

NHC–Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes

“…However, the catalytic activity of the NHC–zinc complex is similar to that of the corresponding alkaline earth and rare earth metal complexes known in the literature. 30–33,34–37…”

“…However, the catalytic activity of the NHC-zinc complex is similar to that of the corresponding alkaline earth and rare earth metal complexes known in the literature. [30][31][32][33][34][35][36][37] To understand the mechanism, we carried out a number of controlled reactions. We conducted an equimolar reaction of the pre-catalyst [Im Dipp Zn(CH 2 CH 3 ) 2 ] with aniline (Ph-NH 2 ) in toluene at room temperature, but we were unable to isolate the active catalyst.…”

“…Several well-designed catalysts have been reported in the literature. 23,31–33 The research groups of Harder, 34 Hill, 35 Trifonov 36 and Carpenteir 37 reported the synthesis of efficient alkaline earth metal (M = Ca, Sr, Ba) complexes as catalysts for CDC reaction. The Sadow group and Schäfer group reported the efficiency of a magnesium (Mg) catalyst in the CDC of aliphatic amines with hydrosilanes.…”

Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers

“…19 It must also be mentioned that a significant number of main group, 24−39 transition metal, 20,21,40−51 and f-block element 52−58 catalysts have been found to mediate the heterodehydrocoupling of amines and silanes to prepare aminosilane monomers. 59 The most active catalyst for Si−N dehydrocoupling reported to date by a significant margin is [Pt(I t Bu') (I t Bu)][BAr F 4 ], (I t Bu = 1,3-di-t-butylimidazolylidene; I t Bu' = the corresponding t-butyl activated metallacycle; Figure 1d). 49 This catalyst was found to mediate Si−N dehydrocoupling with turnover frequencies (TOFs) of up to 330,000 h −1 , more accurately expressed as 5500 min −1 since the trials were conducted over minutes instead of hours, and as 91.7 s −1 for the purpose of this contribution.…”

“…It must also be mentioned that a significant number of main group, − transition metal, ,,− and f-block element − catalysts have been found to mediate the heterodehydrocoupling of amines and silanes to prepare aminosilane monomers . The most active catalyst for Si–N dehydrocoupling reported to date by a significant margin is [Pt­(I t Bu’) (I t Bu)]­[BAr F 4 ], (I t Bu = 1,3-di- t -butylimidazolylidene; I t Bu’ = the corresponding t -butyl activated metallacycle; Figure d) .…”