The reduction of Ag(I) by α‐silylamines R₂NCH₂SiX₃

1-(Methylaminomethyl)silatrane: Synthesis, characterization and reactivity

“…Data of 1 H NMR spectrum of this silatrane presented by the authors are somewhat surprising. As compared to the spectra of 1-(dialkylaminomethyl)silatrane RR 0 NCH 2 Si(OCH 2 CH 2 ) 3 N [22,25,27] the significant downfield shifts of the signals of NCH 3 and NCH 2 Si groups in the 1 H NMR spectrum of this compound takes place. What is the cause of this phenomenon?…”

“…Such changes in the spectra are indicative of quaternization of the exocyclic nitrogen atom and are typical for N-(silatranylmethyl)ammonium salts [22,23,25,40].…”

“…Recently, we have found that the 1-(dialkylaminomethyl)silatrane exhibit enhanced reactivity with respect to polychloromethanes CH n Cl 4Àn [20e23]. They react with alcohols and phenols in inert solvents at room temperature with cleavage of the SieC bond [24], and reduce salts of some metals [25].…”

“…Recently, we have found that the 1-(dialkylaminomethyl)silatrane exhibit enhanced reactivity with respect to polychloromethanes CH n Cl 4Àn [20e23]. They react with alcohols and phenols in inert solvents at room temperature with cleavage of the SieC bond [24], and reduce salts of some metals [25].There is little information on the synthesis, reactivity and structure of 1-(aminomethyl)silatranes RNHCH 2 Si(OCH 2 CH 2 ) 3 N with secondary amino group. Despite the fact that the first representatives of RR 0 NCH 2 Si(OCH 2 CH 2 ) 3 N were obtained in the 70s of the last century [26,27] their molecular and crystal structure remains an unknown.…”

PO → Si intramolecular coordination in the derivatives of 1,4‐phosphasilacyclohexane 1‐oxides

“…However, in spite of apparent simplicity of the scheme above, a number of issues are to be solved and, first of all, it concerns the synthesis of bis(alkylaminomethyl)dialkoxysilanes. Compounds possessing the NCH 2 Si fragment are very reactive as compared to organic amines, e.g., they react with alcohols and phenols in inert solvents at room temperature by splitting of the SiC bond 17, with polyhalogenomethanes to form the corresponding salts (unpublished data), reduce metal cations 18. Therefore, compounds with two such groups may become extremely unstable.…”