Synthesis and Crystal Structures of Three Thioether Functionalized Lithium Silylamides

Abstract

AbstractA series of three lithium silylamides Li2Me2Si(NC6H4‐2‐SR)2 (R=Me, Ph, tBu) were prepared from the reaction of the corresponding silylamines Me2Si(NH‐C6H4‐2‐SR)2 with n‐butyl lithium. X‐ray single crystal structure analyses revealed the formation of dimers [Li4{Me2Si(NC6H4‐2‐SR)2}2] with Si2N4Li4 hetero‐adamantane cores. Recrystallisation of [Li4{Me2Si(NC6H4‐2‐SMe)2}2] and [Li4{Me2Si(NC6H4‐2‐SPh)2}2] from diethyl ether led to the formation of the adducts [Li4(Et2O)2{Me2Si(NC6H4‐2‐SMe)2}2] and [Li4(Et2O){Me2Si(NC6H4‐2‐SPh)2}2]. In the case of the SMe derivative the addition of two diethyl ether molecules led to a rearrangement of the Si2N4Li4 core to give a double decker structure and in contrast the hetero adamantane structure is retained in the diethyl ether adduct of the SPh derivative.