Stoichiometric Reactions of CO 2 and Indium‐Silylamides and Catalytic Synthesis of Ureas

The indium compounds In(N(SiMe 3 ) 2 ) 2 Cl⋅THF ( 2 ) and In(N(SiMe 3 ) 2 )Cl 2 ⋅(THF) n ( 3 ) were shown to react with CO 2 to give [(Me 3 Si) 2 N)InX(μ‐OSiMe 3 )] 2 (X=N(SiMe 3 ) 2 4 , Cl 5 ). 0.05–2.0 mol % of the species 3 acts as a pre‐catalyst for the conversion of aryl and alkyl silylamines under CO 2 (2–3 atm) to give the corresponding ureas in 70–99 % yields. A proposed mechanism is supported by experimental and computational data.