Adsorption of Titanium Tetrachloride on Magnesium Dichloride Clusters

Magnesium
dichloride and titanium tetrachloride are key components
in heterogeneous Ziegler–Natta olefin polymerization catalysis.
We have determined the preferred binding modes of titanium tetrachloride
on magnesium dichloride clusters at the M06-2X level of theory, thus
accounting for dispersion. A systematic study was carried out to locate
the lowest energy isomers of (MgCl2)n(TiCl4)m complexes.
Altogether ca. 1000 complexes with n ranging from
1 to 19 and m from 1 to 13 were studied. In line
with the previous literature, the results consistently show that adsorption
of TiCl4 onto MgCl2 preferably leads to octahedral
six-coordination for both Mg and Ti atoms. This can be achieved by
mononuclear binding of TiCl4 and binuclear binding of Ti2Cl8 on (110) and (104) surfaces of MgCl2, respectively. The preferred octahedral six-coordination is also
achieved by binding of TiCl4 on defect sites, of which
the most striking example is trinuclear binding mode at corners of
the clusters. Overall, the results highlight the relevance of multinuclear
binding of TiCl4 on MgCl2.