Fernández-Baeza, JuanSánchez-Barba, Luis F.Lara-Sánchez, AgustínSobrino, SoniaMartínez-Ferrer, JaimeGarcés, AndrésNavarro, MartaRodríguez, Ana M.2020-12-152020-12-152020Inorg. Chem. 2020, 59, 17, 12422–124301520-510Xhttp://hdl.handle.net/10115/17340PreprintTwo new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily prepared. We verified the potential utility of these compounds through the reaction with [Zr(NMe2)4] for the preparation of novel zirconium complexes in which an ancillary bis(pyrazol-1-yl)methanide acts as a robust monoanionic tridentate scorpionate in a κ3-NNC chelating mode, forming strained four-membered heterometallacycles. These κ3-NNC-scorpionate zirconium amides were investigated as catalysts in combination with tetra-n-butylammonium bromide as cocatalyst for CO2 fixation into five-membered cyclic carbonate products. The study has led to the development of an efficient zirconium-based bicomponent system for the selective cycloaddition reaction of CO2 with epoxides. Kinetics investigations confirmed apparent first-order dependence on the catalyst and cocatalyst concentrations. In addition, this system displays very broad substrate scope, including mono- and disubstituted substrates, as well as the challenging biorenewable terpene derived limonene oxide, under mild and solvent-free conditions.engAttribution-NonCommercial-NoDerivatives 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/QuímicazincscorpionatesCO2info:eu-repo/semantics/preprint10.1021/acs.inorgchem.0c01532info:eu-repo/semantics/openAccess23 Química