Efficient CO 2 Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex

The terminal zinc hydride complex [Tntm]ZnH ( 2 ; Tntm=tris(6‐tert‐butyl‐3‐thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO 2 at room temperature without the need of Lewis acidic additives. The inherent electrophilicity of the system leads to selective formation of the monosilylated product (MeO) 3 SiO 2 CH (at room temperature with a TOF of 22.2 h −1 and at 45 °C with a TOF of 66.7 h −1 ). In absence of silanes, the intermediate formate complex [Tntm]Zn(O 2 CH) ( 3 ) is quantitatively formed within 5 min. All complexes were fully characterized by 1 H and 13 C NMR spectroscopy and single‐crystal X‐ray diffraction analyses. Density functional theory (DFT) calculations reveal a high positive charge on zinc and the increased preference of the ligand to adopt a κ 3 ‐coordination mode.