Heterogenization of [Ti(η5-C5HMe4)Cl3] on to MCM-41 and organomodified MCM-41 to form epoxidation catalyst

Pérez, Yolanda; Ballesteros, Ruth; Fajardo, Mariano; Sierra, Isabel; Hierro, Isabel del

doi:10.1016/j.jorganchem.2010.12.014

“…The titanium loading values for the immobilized titanium complexes Ti‐amine‐bis(phenolate)‐SBA‐15 and Ti‐amine‐bis(phenolate)‐HMDS‐SBA‐15, calculated on the basis of experimental XRF analysis, are 0.27 and 0.21 mmol g −1 ; these are low values in comparison to those of other titanium supported materials previously reported by our group . This can be explained by the high steric hindrance imposed by the ligands.…”

Section: Resultsmentioning

confidence: 63%

Heterogenization of titanium(IV) complexes with amine bis(phenolate) ligands onto SBA‐15: exploring their catalytic epoxidation and electrochemical behaviour

Hierro

¹

,

Pérez

²

,

Fajardo

³

2016

Applied Organom Chemis

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This paper describes the synthesis and characterization of titanium catalysts supported onto SBA‐15 via chemical bonding. This was done by first modifying the support with amine bis(phenol) groups as functional linkers and hexamethyldisilizane as capping agent to mask the remaining silanol groups on the silica surface. Finally, titanium tetraisopropoxide was immobilized by reaction with the modified SBA‐15. All the materials were characterized using X‐ray diffraction, X‐ray fluorescence, nitrogen adsorption‐desorption, Fourier transform infrared, UV‐visible diffuse reflectance and solid‐state nuclear magnetic resonance spectroscopies, and solid‐state electrochemical techniques. The titanium materials were tested as cyclohexene epoxidation catalysts. The stability and reusability of the catalysts were also examined using voltammetry measurements. Copyright © 2016 John Wiley & Sons, Ltd.

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“…Perez et al [119] described the introduction of [Ti(η 5 -C 5 HMe 4 )Cl 3 ] on MCM-41 mesoporous silica using two pathways: Method A: modification of the silica surface with a ligand useful to bind the active metal complex; and Method B: direct immobilization of the metal precursor on the MCM-41 support (Figure 8). Besides a classical procedure involving the modification of the siliceous support with different silanes (triazine propyl triethoxysilane TPTS and methyltrimethoxysilane MTMS (MeSi(OMe) 3 ) or hexamethyldisilizane HMDS (HN-(SiMe 3 ) 2 ), the authors proposed as an alternative, a one-step modification of the support with [Ti(η 5 -C 5 HMe 4 )Cl 3 ] and MTMS or HDMS.…”

Section: Metallocenesmentioning

confidence: 99%

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions**

Bisio

¹

,

Carniato

²

2022

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This Review provides a summary of the use and the role of coordination complexes as precursors for the generation of heterogeneous catalysts for oxidation reactions of interest for fine chemical synthesis. Specific attention is paid to the comprehension of phenomena explaining the formation of active sites in heterogeneous catalysts. Different families of coordination precursors are considered. For each example, a brief critical description of the synthesis, characterization, and catalytic performance is reported. Special attention is paid to the chemical environment of the first coordination sphere of the active metal centre. The catalysts obtained by heterogenization, grafting, or anchoring of homogeneous catalysts can therefore exhibit enhanced catalytic performance by merging advantages of both homogeneous and heterogeneous systems. The deposition of coordination complexes over a preformed support is indeed a conceptually versatile strategy to design novel catalysts with tuned and controlled properties.

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“…Perez et al [119] . described the introduction of [Ti( η 5 ‐C 5 HMe 4 )Cl 3 ] on MCM‐41 mesoporous silica using two pathways: Method A: modification of the silica surface with a ligand useful to bind the active metal complex; and Method B: direct immobilization of the metal precursor on the MCM‐41 support (Figure 8).…”

Section: Overview Of Supported Metal Complexes For Oxidation Reactionsmentioning

confidence: 99%

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions**

Bisio

¹

,

Carniato

²

2022

Angewandte Chemie

0

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This Review provides a summary of the use and the role of coordination complexes as precursors for the generation of heterogeneous catalysts for oxidation reactions of interest for fine chemical synthesis. Specific attention is paid to the comprehension of phenomena explaining the formation of active sites in heterogeneous catalysts. Different families of coordination precursors are considered. For each example, a brief critical description of the synthesis, characterization, and catalytic performance is reported. Special attention is paid to the chemical environment of the first coordination sphere of the active metal centre. The catalysts obtained by heterogenization, grafting, or anchoring of homogeneous catalysts can therefore exhibit enhanced catalytic performance by merging advantages of both homogeneous and heterogeneous systems. The deposition of coordination complexes over a preformed support is indeed a conceptually versatile strategy to design novel catalysts with tuned and controlled properties.

show abstract

Heterogenization of [Ti(η5-C5HMe4)Cl3] on to MCM-41 and organomodified MCM-41 to form epoxidation catalyst

Cited by 10 publications

References 42 publications

Heterogenization of titanium(IV) complexes with amine bis(phenolate) ligands onto SBA‐15: exploring their catalytic epoxidation and electrochemical behaviour

Heterogenization of titanium(IV) complexes with amine bis(phenolate) ligands onto SBA‐15: exploring their catalytic epoxidation and electrochemical behaviour

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions**

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions**

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