^MeCAAC=N⁻: A Cyclic (Alkyl)(Amino)Carbene Imino Ligand

Abstract

Abstract A cyclic (alkyl)(amino)carbene (CAAC) has been shown to react with a covalent azide similar to the Staudinger reaction. The reaction of Me CAAC with trimethylsilyl azide afforded the N‐silylated 2‐iminopyrrolidine ( Me CAAC=NSiMe 3 ), which was fully characterized. This compound undergoes hydrolysis to afford the 2‐iminopyrrolidine and trimethylsiloxane which co‐crystallize as a hydrogen‐bonded adduct. The N‐silylated 2‐iminopyrrolidine was used to transfer the novel pyrrolidine‐2‐iminato ligand onto both main‐group and transition‐metal centers. The reaction of the tetrabromodiborane bis(dimethyl sulfide) adduct with two equivalents of Me CAAC=NSiMe 3 afforded the disubstituted diborane. The reaction of Me CAAC=NSiMe 3 with TiCl 4 and CpTiCl 3 afforded Me CAAC=NTiCl 3 and Me CAAC=NTiCl 2 Cp, respectively.