Calculations of hydrated titanium ion complexes: structure and influence of the first two coordination spheres

Uudsemaa, Merle; Tamm, Toomas

doi:10.1016/s0009-2614(01)00617-0

Cited by 21 publications

(30 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As expected, hydrogen bonds are broken during the geometry optimisation, and a proton is transferred from the first to the second hydration shell (Uudsemaa and Tamm, 2001). This predicts that for example species such as [TiOH(H 2 O) 5 ] 3+ are likely to be present in aqueous solution, in agreement with the indirectly obtained experimental results for acidic solutions.…”

Section: Coordination Of Ti In Aqueous Fluidssupporting

confidence: 85%

“…Bond-length estimates from combined X-ray and TEM measurements as well as static embedded cluster calculations on four-and six-fold coordinated titanium water complexes are in excellent agreement with these results (Gatehouse et al, 1993;Uudsemaa and Tamm, 2001).…”

Section: Titanium Coordinationsupporting

confidence: 73%

“…Theoretical investigations using a variety of static quantum chemical (embedded) cluster calculations support the experimentally observed six-fold coordination of Ti(IV) with water (Tachikawa et al, 1990;Å kesson et al, 1992Rotzinger, 1996;Hartmann et al, 1999;Uudsemaa and Tamm, 2001;Bock et al, 2006). As expected, hydrogen bonds are broken during the geometry optimisation, and a proton is transferred from the first to the second hydration shell (Uudsemaa and Tamm, 2001).…”

Section: Coordination Of Ti In Aqueous Fluidssupporting

confidence: 63%

“…This predicts that for example species such as [TiOH(H 2 O) 5 ] 3+ are likely to be present in aqueous solution, in agreement with the indirectly obtained experimental results for acidic solutions. Ti-OH distances are short (1.72 Å ) compared to the average Ti-O distance (2.05 Å ) of the five first shell water molecules (Uudsemaa and Tamm, 2001;Bock et al, 2006) and the associated hydronium (H 3 O + ) species is found far (>14 Å ) from the central titanium (Bock et al, 2006). The simulated bond lengths are in good agreement with those observed experimentally in for instance titanyl sulphate (TiOSO 4 ), where reported Ti-O bonds lengths are on average 1.7 and 2.05 Å , respectively (Gatehouse et al, 1993).…”

Section: Coordination Of Ti In Aqueous Fluidsmentioning

confidence: 86%

See 3 more Smart Citations

Titanium in subduction zone fluids: First insights from ab initio molecular metadynamics simulations

Sijl

Allan

Davies

et al. 2010

Geochimica et Cosmochimica Acta

View full text Add to dashboard Cite

Section: Coordination Of Ti In Aqueous Fluidssupporting

confidence: 85%

Section: Titanium Coordinationsupporting

confidence: 73%

Section: Coordination Of Ti In Aqueous Fluidssupporting

confidence: 63%

Section: Coordination Of Ti In Aqueous Fluidsmentioning

confidence: 86%

See 2 more Smart Citations

Titanium in subduction zone fluids: First insights from ab initio molecular metadynamics simulations

Sijl

Allan

Davies

et al. 2010

Geochimica et Cosmochimica Acta

View full text Add to dashboard Cite

“…2 Therefore many studies appeared on complexes, which are active against cancer cells. Various biophysical and biochemical properties of rhodium, 3-7 titanium, [8][9][10] ruthenium, [11][12][13][14][15][16][17][18][19][20][21][22][23][24] and many other metal complexes 25,26 were explored.…”

Section: Introductionmentioning

confidence: 99%

Comparison of hydration reactions for “piano-stool” RAPTA-B and [Ru(η6− arene)(en)Cl]+ complexes: Density functional theory computational study

Chval¹,

Futera

Burda

2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl(2) (from the RAPTA family) and [Ru(arene)(en)Cl](+) (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP∕6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt∕Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal∕mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

show abstract

Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?

Moens

Roos

Jaque

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

Previous contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car-Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc(3+) | Sc(2+) to Cu(3+) | Cu(2+)) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non-reactive continuum region.

show abstract

Calculations of hydrated titanium ion complexes: structure and influence of the first two coordination spheres

Cited by 21 publications

References 14 publications

Titanium in subduction zone fluids: First insights from ab initio molecular metadynamics simulations

Titanium in subduction zone fluids: First insights from ab initio molecular metadynamics simulations

Comparison of hydration reactions for “piano-stool” RAPTA-B and [Ru(η6− arene)(en)Cl]+ complexes: Density functional theory computational study

Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?

Contact Info

Product

Resources

About