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…