02146nas a2200289   4500008004100000022001400041245013400055210006900189260000900258300001200267490000700279520117400286653000801460653001101468653003001479653002301509653002801532100001501560700001901575700002101594700002601615700002501641700002701666700001701693700002301710856012301733       2021                        eng d  a1867-388000aInsights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study0 aInsights into the nature of selfextinguishing external donors fo  cJAN   a674-6810 v133 a<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 ` 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>
10aDFT10adonors10anon-covalent interactions10aself-extinguishing10aZiegler-Natta catalysis1 aRaj, Vipin1 aKumawat, Jugal1 aDhamaniya, Sunil1 aSubaramanian, Murugan1 aBalaraman, Ekambaram1 aGupta, Virendra, Kumar1 aVanka, Kumar1 aGrubbs, Robert, H.  uhttps://library.ncl.res.in/content/insights-nature-self-extinguishing-external-donors-ziegler-natta-catalysis-combined02184nas a2200205   4500008004100000022001400041245014300055210007000198260000800268490000700276520142000283653002001703653002601723653003001749653001501779653000901794100002501803700001701828856013301845       2024                        eng d  a1439-423500aExploring unconventional σ-hole interactions: computational insights into the interaction of XeO3 with non-aromatic coordinating solvents0 aExploring unconventional σhole interactions computational insigh  cMAR0 v253 a<p>
	In order to control the explosiveness and shock sensitivity of XeO3, we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO3 was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules. The C-H &amp; mldr;O interactions were also found to be a contributing factor in the stabilization of these adducts. Although these aerogen-bonding interactions were found to be predominantly electrostatic, significant contributions from the orbital contributions, as well as dispersion interactions, were observed. The top three non-aromatic solvents (among the twenty six studied) which form the strongest adducts with XeO3 are proposed to be hexamethylphosphoramide (HMPA), N,N `-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA).</p>
10aAerogen bonding10aNon-Aromatic Solvents10anon-covalent interactions10aSigma-hole10aXeO31 aDash, Soumya, Ranjan1 aVanka, Kumar  uhttps://library.ncl.res.in/content/exploring-unconventional-%CF%83-hole-interactions-computational-insights-interaction-xeo3-non