Disclosing the Interaction between Carbon Monoxide and Alkylated Ti(3+) Species: a Direct Insight into Ziegler–Natta Catalysis

[Image: see text] In the field of Ziegler–Natta catalysis for olefin polymerization, carbon monoxide (CO) is used in the industrial practice to quench the reaction when it proceeds too fast, approaching critical levels for the plant safety. The quenching effect is explained as due to the reversible coordination of CO to the titanium active sites, but no direct evidence has been ever reported. In this work, we designed a series of experiments to monitor CO adsorption at variable temperatures on a model Ziegler–Natta catalyst by means of FT-IR spectroscopy. For the first time, we have been able to spectroscopically detect CO coordinated to alkylated Ti(3+) sites and the Ti–acyl species formed upon the subsequent insertion of CO into the Ti(3+)–alkyl bond, both in the absence and in the presence of the olefin monomer. In perspective, this has important implications for the characterization of the active sites in industrial Ziegler–Natta catalysts, even under working conditions.