A zirconocene triazenido hydride complex activates CO2

Abstract

Starting from the alkyne complex Cp₂Zr(py)(η²-Me₃SiC₂SiMe₃) (Cp = η⁵-cyclopentadienyl, py = pyridine), the synthesis and complete characterisation of a zirconocene(IV) triazenido hydride complex and its use in the activation of small molecules is reported. The reaction with CO₂ led to the formation of a zirconocene(IV) triazenido-formate complex, which was further investigated for its stability towards different bases with respect to the formation of formic acid. The experimentally observed reaction pathway was investigated computationally using DFT methods, revealing the favourable role of pyridine coordination in the hydrogen transfer from the triazene to the alkyne unit of the zirconocene reagent.