Base-catalyzed cleavage and homologation of polyhedral oligosilsesquioxanes

Feher, Frank J.; Terroba, Raquel; Ziller, Joseph W.

doi:10.1039/a906397h

Cited by 62 publications

(45 citation statements)

References 31 publications

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“…There are, however, only a limited number of metal-containing silsesquioxanes with such functional groups [39,45,48,64,65]. Earlier works by Feher's group show a preparative method of silsesquioxane silanols with alkenylsilyl functionality via an indirect route [64,65]. The present authors successfully prepared alkenylsilyl-substituted silanols by the kinetically controlled direct silylation, and transformed them to metal-containing ones, such as Cp¢ 2 M[(c-C 5 [48,39].…”

Section: Preparation Of Immobilized and Polymeric Catalysts Utilizingmentioning

confidence: 84%

“…alkenylsilyl or alkoxysilyl groups, is of importance. There are, however, only a limited number of metal-containing silsesquioxanes with such functional groups [39,45,48,64,65]. Earlier works by Feher's group show a preparative method of silsesquioxane silanols with alkenylsilyl functionality via an indirect route [64,65].…”

Section: Preparation Of Immobilized and Polymeric Catalysts Utilizingmentioning

confidence: 97%

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Preparation of Novel Materials for Catalysts Utilizing Metal-Containing Silsesquioxanes

Wada

Mitsudo

2005

Catal Surv Asia

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Recent progress of the preparation of novel materials for catalysts utilizing metal-containing silsesquioxanes are reviewed in the following categories: (i) activities of vanadium or titanium-containing silsesquioxanes as homogeneous catalysts for oxidative reactions, (ii) preparation of immobilized or polymeric catalysts, and (iii) preparation of porous oxide catalysts utilizing metalcontaining silsesquioxanes. The present authors found that the liquid phase photo-oxidation of cyclohexane in the presence of a vanadium-containing silsesquioxane as a homogeneous catalyst selectively afforded cyclohexanol and cyclohexanone in high yields. Facile synthetic methods for group 4 metal-containing silsesquioxanes with functionalized silyl (or germyl) groups are presented. Remarkably, titanocene(IV)-containing silsesquioxanes have been synthesized for the first time. The presence of alkenylsilyl substituents shows a promotional effect on the epoxidation of cycloalkenes, which was found to be more significant for titaniumbridged silsesquioxanes. By utilizing these silsesquioxanes, polymeric, starburst-like, and dendritic silsesquioxanes were prepared as well as novel caged or macrocyclic molecules with organic-inorganic hybrid structures. The controlled calcination of these metalcontaining silsesquioxanes at around 823 K produces porous oxides with high BET surface areas of 300-520 m 2 g )1 and uniformlycontrolled micropores of 0.5-0.6 nm diameter. The oxides are found to include a well-dispersed metallic oxide species. From group 13 elements-containing silsesquioxanes Bro¨nsted acidic oxides are produced. Among them, aluminum-containing oxides show excellent activities for the cracking of cumene even at low temperature, 523 K, in spite of their amorphous nature.

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Section: Preparation Of Immobilized and Polymeric Catalysts Utilizingmentioning

confidence: 84%

Section: Preparation Of Immobilized and Polymeric Catalysts Utilizingmentioning

confidence: 97%

Preparation of Novel Materials for Catalysts Utilizing Metal-Containing Silsesquioxanes

Wada

Mitsudo

2005

Catal Surv Asia

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“…Vinyl silsesquioxane trisilanol [(H 2 C=CH)( c ‐C 6 H 11 ) 6 Si 7 O 9 (OH) 3 ] ( 1 )9 can be easily converted to new titanium silsesquioxane complexes [(H 2 C=CH)( c ‐C 6 H 11 ) 6 Si 7 O 12 TiX] ( 2 a , X= η 5 ‐C 5 H 5 (Cp), 2 b , X=O i Pr) by reaction with [Cl 3 TiCp] or [Ti(O i Pr) 4 ], respectively . These reactions are similar to those previously described for the related, unfunctionalized silsesquioxane trisilanol [( c ‐C 6 H 11 ) 7 Si 7 O 9 (OH) 3 ] 6b, 10.…”

Section: Methodsmentioning

confidence: 99%

Titanium Silsesquioxanes Grafted on Three-Dimensionally Netted Polysiloxanes: Catalytic Ensembles for Epoxidation of Alkenes with Aqueous Hydrogen Peroxide

et al. 2002

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“…Furthermore, incompletely condensed POSS compounds have shown to be ideal for modeling various silica surfaces, surface silanol sites, and silica-supported catalysts Herrmann et al 1994). Incompletely condensed cages can be prepared via incomplete hydrolysis of reactive silanes (Brown 1965), or as shown in Scheme 2, by ring-opening fully condensed cages (Feher et al 1998(Feher et al , 1999.…”

Section: Incompletely Condensed Possmentioning

confidence: 99%

Polyhedral Silsesquioxanes

Jennings¹,

Iacono²,

Mabry³

2016

Handbook of Sol-Gel Science and Technology

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This chapter aims to highlight the selected applications of polyhedral oligomeric silsesquioxanes (POSS). A brief introduction will be given and used to highlight the use of solution-gelation chemistry for the synthesis of POSS. Furthermore, the different three-dimensional structures, including fully and incompletely condensed, random, and ladder structures, will be discussed. Subsequently, the use of the various POSS structures as fillers in polymeric nanocomposites will be examined, with a focus on polymer blends, pendant polymers, bead polymers,

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Base-catalyzed cleavage and homologation of polyhedral oligosilsesquioxanes

Cited by 62 publications

References 31 publications

Preparation of Novel Materials for Catalysts Utilizing Metal-Containing Silsesquioxanes

Preparation of Novel Materials for Catalysts Utilizing Metal-Containing Silsesquioxanes

Titanium Silsesquioxanes Grafted on Three-Dimensionally Netted Polysiloxanes: Catalytic Ensembles for Epoxidation of Alkenes with Aqueous Hydrogen Peroxide

Polyhedral Silsesquioxanes

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