Insights into the Nature of Self‐Extinguishing External Donors for Ziegler-Natta Catalysis: A Combined Experimental and DFT Study

Developing donors for Ziegler‐Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi‐component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D₁ (2,2,2‐trifluoroethyl myristate) and D₂ (2,2,2‐trifluoroethyl palmitate) that show self‐extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D₁ and D₂ can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self‐extinguishing nature. The non‐covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors′ self‐extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self‐extinguishing donors function in ZN catalytic systems.