Synthesis and Crystal Structures of Three Thioether Functionalized Lithium Silylamides

Abstract A series of three lithium silylamides Li 2 Me 2 Si(NC 6 H 4 ‐2‐SR) 2 (R=Me, Ph, t Bu) were prepared from the reaction of the corresponding silylamines Me 2 Si(NH‐C 6 H 4 ‐2‐SR) 2 with n ‐butyl lithium. X‐ray single crystal structure analyses revealed the formation of dimers [Li 4 {Me 2 Si(NC 6 H 4 ‐2‐SR) 2 } 2 ] with Si 2 N 4 Li 4 hetero‐adamantane cores. Recrystallisation of [Li 4 {Me 2 Si(NC 6 H 4 ‐2‐SMe) 2 } 2 ] and [Li 4 {Me 2 Si(NC 6 H 4 ‐2‐SPh) 2 } 2 ] from diethyl ether led to the formation of the adducts [Li 4 (Et 2 O) 2 {Me 2 Si(NC 6 H 4 ‐2‐SMe) 2 } 2 ] and [Li 4 (Et 2 O){Me 2 Si(NC 6 H 4 ‐2‐SPh) 2 } 2 ]. In the case of the SMe derivative the addition of two diethyl ether molecules led to a rearrangement of the Si 2 N 4 Li 4 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.