1999
DOI: 10.1021/ja983339i
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Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br)

Abstract: Ab initio calculations have been performed on the closed-shell molecules TiX4 and Ti2X8 (X = F, Cl, Br) in order to determine the magnitude and the nature of the intermolecular self-interactions of the titanium tetrahalides. Geometry optimizations have been carried out using an effective core potential basis set with polarization, including the effects of dynamic electron correlation through second-order perturbation theory (MP2). The importance of higher order correlation effects is examined through coupled c… Show more

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Cited by 29 publications
(28 citation statements)
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“…Lower level calculations are also in agreement. 49 The Ti-Cl bond distances in TiCl 3 OH, TiOCl 2 , TiOClOH, TiCl 2 (OH) 2 , and TiCl(OH) 3 are predicted to lengthen from that in TiCl 4 with an increase in the number of O atoms and with changes in the number of ligands bonded to the Ti atom. The Ti-Cl bond distance in TiOCl 2 of 2.234 Å calculated 26 at the B97-1/6-311+G(d,p) level is shorter than our CCSD(T)/aVTZ value by ∼0.02 Å.…”
Section: Resultsmentioning
confidence: 98%
“…Lower level calculations are also in agreement. 49 The Ti-Cl bond distances in TiCl 3 OH, TiOCl 2 , TiOClOH, TiCl 2 (OH) 2 , and TiCl(OH) 3 are predicted to lengthen from that in TiCl 4 with an increase in the number of O atoms and with changes in the number of ligands bonded to the Ti atom. The Ti-Cl bond distance in TiOCl 2 of 2.234 Å calculated 26 at the B97-1/6-311+G(d,p) level is shorter than our CCSD(T)/aVTZ value by ∼0.02 Å.…”
Section: Resultsmentioning
confidence: 98%
“…Although TiCl 4 provides excellent control over the cleavage/alkylation reaction, with low rate of undesired side‐reactions, such as carbocation rearrangement, it must be used in relatively high concentrations to achieve adequate overall rate of cleavage/alkylation. Moreover, the concentration of Ti 2 Cl 8 dimer, which is the species active in ionization, is governed by an equilibrium that is exothermic in the forward direction, and therefore its concentration decreases with increasing temperature . We expect this to partially or possibly completely offset any rate increases for the overall cleavage/alkylation process that might be achieved by increases in temperature.…”
Section: Resultsmentioning
confidence: 98%
“…The calculations were performed using a cubic supercell with side of 16 Bohr radii, in order to minimize interactions among images. A TiÀCl bond length of 2.177 is obtained and compared with the experimental [23] value of 2.170 and with the theoretical [24] result of 2.171 , obtained at the MP2 level. The vibrational harmonic frequencies resulted at 139, 159, 387 and 501 cm…”
mentioning
confidence: 82%