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

The introduction of the organosilicon substituent into the α‐position of an amino group results in cardinal change of the amine reactivity irrespective of the coordination state of silicon. Amines R₂NCH₂SiX₃ [R = Me, Et, PhCH₂, CH₂SiX₃; SiX₃ = SiMe₃, Si(OEt)₃, Si(OCH₂CH₂)₃N] easily react with AgNO₃, to give the corresponding ammonium salts (R₂NH⁺ CH₂SiX₃)·NO₃^?. At the same time, Ag(I) is reduced to Ag(0). The interaction of N‐methyl‐N,N‐bis(silatranylmethyl)amine with AgNO₃ has been investigated by EPR spectroscopy. It was proven that the reaction involved a single electron transfer stage with the formation of cation radical of this amine. A mechanism of the reaction is proposed. Copyright © 2006 John Wiley & Sons, Ltd.