Group 4 Complexes Bearing Pyrrolide Ligand for Intramolecular Alkene Hydroamination and Activation of C≡N Bond

Titanium and zirconium complexes supported by a pyrrolide ligand HL1 [HL1 = 2‐cyano‐1H‐pyrrole], Ti2(L2)2(NMe2)2 (1) and Zr3(L2)3(NMe2)6 (2) [L2 = N,N‐dimethyl‐1H‐pyrrol‐2‐carboximidamide, NMe2‐L1] were synthesized and characterized. The ligand L2 was generated by activation of C≡N bond of HL1 with HNMe2. In complex 1, two TiIV atoms are bridged by two nitrogen atoms. There are three characteristic ZrIV ions in 2, which are six‐, seven‐ and six‐coordinate, respectively. They were tested as catalysts for the intramolecular hydroamination of aminoalkenes, and the respective N‐heterocycles were afforded in 74–99 % yields. Moreover, the formation of L2 ligand indicates that the amination of C≡N bond can be considered as a new and rapid way to synthesize other C–N bonds.