02845nas a2200181   4500008004100000022001400041245013600055210006900191260007100260300001600331490000800347520210200355100001702457700001902474700001602493700002402509856013002533       2010                        eng d  a1932-744700aDFT Study of lewis base interactions with the MgCl2 surface in the ziegler-natta catalytic system: expanding the role of the donors0 aDFT Study of lewis base interactions with the MgCl2 surface in t  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP  a15771-157810 v1143 a<p>We present a computational study, using density functional theory, of the role of internal and external donors in supported heterogeneous Ziegler-Natta polymerization catalyst systems. The focus of the investigation is the ability of the donors to stabilize the MgCl2 support through the zip mode of coordination. Phthalates and alkoxy benzoates have been considered as representative internal and external donors, respectively. Models for the alpha (ccp) and the beta (hcp) phases of the (110) MgCl2 lateral cut have been considered. Studies were first done with a ``Fully Fixed Model'', where the atoms in the MgCl2 lateral cuts were kept fixed. The studies indicated that the phthalate donors would preferentially stabilize the alpha phase of MgCl2, while the alkoxy benzoate donors would stabilize the beta phase more, corroborating experimental results. A comparison of the zip coordination mode with other modes of coordination (mono, chelate, and bridge) indicates that it would be preferred over the mono and chelate coordination modes and be competitive with the bridge coordination mode. The validity of the Fully Fixed Model was then tested by doing calculations with the Partially Relaxed (some of the magnesium and chlorine atoms unfixed) and the Fully Relaxed (all atoms free) Models. The results from the latter two models corrected some of the discrepancies that had been observed for the Fully Fixed Model in comparison to previous experimental and computational investigations but were in general agreement with the Fully Fixed Model, indicating that the overall conclusions drawn with the earlier model are correct. Insertion studies done on an octahedrally coordinated titanium site flanked by two zip-coordinated phthalate donor molecules indicated that the zip-coordinating donors can confer exceptional regioselectivity to the titanium center. A list of potential donors that could serve as external donors, with di-iso-butyl phthalate (DIBP) as the internal donor, was investigated, and it was found that 1,3-diethers would serve as the best external donors to DIBP.</p>1 aVanka, Kumar1 aSingh, Gurmeet1 aIyer, Divya1 aGupta, Virendra, K.  uhttps://library.ncl.res.in/content/dft-study-lewis-base-interactions-mgcl2-surface-ziegler-natta-catalytic-system-expanding-0