Novel unusually stable peroxotitanium(IV) compounds. Molecular and crystal structure of peroxobis(picolinato)(hexamethylphosphoric triamide)titanium(IV)

Mimoun, Hubert; Postel, M.; Casabianca, Francis.; Fischer, J.; Mitschler, A.

doi:10.1021/ic00134a004

Cited by 64 publications

(26 citation statements)

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“…Added H20 does not influence the chemical shifts of either PWnTiO or PWllTiO2. It should be noted that the most known peroxotitanium complexes appeared to be unreactive toward organic substrates [9]. At the same time, titanium silicates, such as TS-1 and TS-2, were found to be very efficient catalysts for selective oxidation reactions with dilute H202 [10][11][12][13][14].…”

Section: Resultsmentioning

confidence: 99%

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Kholdeeva

Maksimovskaya

Maksimov

et al. 1998

React Kinet Catal Lett

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Section: Resultsmentioning

confidence: 99%

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Kholdeeva

Maksimovskaya

Maksimov

et al. 1998

React Kinet Catal Lett

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“…This enhanced lability is strongly supported by studies of metal oxo chemistry, where the addition of a peroxo ligand has been shown to stabilize five-coordinate Ti clusters in solution over the more common six-coordinate species. 20 This effect is important in etching, where the near-simultaneous cleavage of multiple bulk bonds is required.…”

Section: Peroxo Ligands and Reactivitymentioning

confidence: 99%

Rutile Surface Reactivity Provides Insight into the Structure-Directing Role of Peroxide in TiO₂Polymorph Control

2014

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The peroxo ligand is one of the most promising structure-directing agents in TiO 2 nanocatalyst synthesis; however, its role in nanocatalyst growth and polymorph control is not well understood. Using a combination of scanning tunneling microscopy, X-ray photoemission spectroscopy, and kinetic Monte Carlo simulation, we show that the base-catalyzed reaction of H 2 O 2 targets very particular sites on the rutile (110) surface, sites that are present in concentrations of less than 1% of a monolayer, producing highly homogeneous surfaces characterized by flat terraces and straight atomic-height steps. This reaction produces surface steps with a different orientation, different structure, and different reactivity from those prepared in ultrahigh vacuum studies. The observed reactivity is explained by a simple, site-specific model that is based on metal oxo coordination chemistry. This study shows that one of the principle roles of peroxide in etching and growth reactions is destabilizing neighboring bonds and increasing their lability. As a result, the peroxo ligand adds a degree of reversibility to growth reactions, thereby promoting the formation of well ordered crystals.

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“…MoO5HMPT + S ~ MoO5HMPT,S, K'AS s (32) MoO5HMPT + HMPT ~ MoO5(HMPT) 2, K"ASS (33) MoO5HMPT + 2S ~ MoO5(S) 2 + HMPT, K'"ASS (34) Scheme 19 In all the equilibria of Scheme …”

Section: Tionsmentioning

confidence: 99%

Peroxometal complexes

Furia

Modena

1985

Res Chem Intermed

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Novel unusually stable peroxotitanium(IV) compounds. Molecular and crystal structure of peroxobis(picolinato)(hexamethylphosphoric triamide)titanium(IV)

Cited by 64 publications

References 1 publication

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Rutile Surface Reactivity Provides Insight into the Structure-Directing Role of Peroxide in TiO₂Polymorph Control

Peroxometal complexes

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Novel unusually stable peroxotitanium(IV) compounds. Molecular and crystal structure of peroxobis(picolinato)(hexamethylphosphoric triamide)titanium(IV)

Cited by 64 publications

References 1 publication

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Oxidation of methyl phenyl sulfide with hydrogen peroxide catalyzed by Ti(IV)-substituted heteropolytungstate

Rutile Surface Reactivity Provides Insight into the Structure-Directing Role of Peroxide in TiO2Polymorph Control

Peroxometal complexes

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Product

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Rutile Surface Reactivity Provides Insight into the Structure-Directing Role of Peroxide in TiO₂Polymorph Control