@article {46630,
	title = {Insights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study},
	journal = {ChemCatChem},
	volume = {13},
	year = {2021},
	month = {JAN },
	pages = {674-681},
	type = {Article},
	abstract = {<p>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, D-1 (2,2,2-trifluoroethyl myristate) and D-2 (2,2,2-trifluoroethyl palmitate) that show self-extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D-1 and D-2 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 {\textquoteleft} 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.</p>
},
	keywords = {DFT, donors, non-covalent interactions, self-extinguishing, Ziegler-Natta catalysis},
	issn = {1867-3880},
	doi = {10.1002/cctc.202001493, Early Access Date = NOV 2020},
	author = {Vipin Raj, K. and Kumawat, Jugal and Dhamaniya, Sunil and Subaramanian, Murugan and Balaraman, Ekambaram and Kumar Gupta, Virendra and Vanka, Kumar and Grubbs, Robert H.}
}
