Synthesis and crystal structures of bromo- and ester-functionalised polyhedral silsesquioxanes

Drylie, Ewan A.; Andrews, Christopher; Hearshaw, Meredith A.; Jiménez-Rodríguez, Cristina; Slawin, Alexandra M. Z.; Cole‐Hamilton, David J.; Morris, Russell E.

doi:10.1016/j.poly.2005.09.007

Cited by 16 publications

(11 citation statements)

References 20 publications

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“…V 8 T 8 is a commercially available, very useful POSS derivative. The vinyl group can undergo many chemical transformations, including hydrobromination,28 epoxidation,17c olefin metathesis,29 Heck coupling,30 hydrosilylation,31 phosphination,32 and the thiol–ene reaction 33. Among them, thiol–ene chemistry has been demonstrated as an effective way not only to prepare monofunctionalized POSS,20a but also for rapid diversification of the POSS surface chemistry from a common precursor, which is indispensable in creating libraries of model compounds 10b.…”

Section: Resultsmentioning

confidence: 99%

Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Wang

Guo

Han

et al. 2015

Chemistry A European J

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Precise synthesis of nanobuilding blocks with accurately positioned functional groups presents a daunting challenge. Herein, a practical synthesis and thorough characterization of a series of T8 -polyhedral oligomeric silsesquioxane (POSS) di- and triadducts is reported. Upon addition of triflic acid across the double bonds in octavinylPOSS (V8 T8 ) followed by hydrolysis, the cubic symmetry of the T8 -POSS cage (Oh ) is broken into C2v (ortho-), C2v (meta-), and D3d (para-) for diadducts and further to Cs (oom-), Cs (omp-), and C3v (mmm-) for triadducts in a stochastic fashion. Their structures and regioconfigurations have been unambiguously demonstrated by (1) H, (13) C, and (29) Si NMR spectroscopy, as well as MALDI-TOF mass spectrometry. The assignment of the diadducts was further corroborated by converting each individual diadduct into triadduct(s), the structure of which is controlled by the symmetry of the precursor. Except for the C3v triadduct, they can all be prepared in synthetically useful quantities. The presence of two types of highly reactive and mutually orthogonal functional groups facilitates further modification into complex nanostructures and composite materials. These unique regioisomers provide a versatile platform for constructing giant molecules and Janus silsesquioxanes.

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Section: Resultsmentioning

confidence: 99%

Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Wang

Guo

Han

et al. 2015

Chemistry A European J

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“…The functionalization of silsesquioxanes with ester or acid groups opens potential for further functionalization to novel molecules. 1,2-DTBPMB was chosen as a ligand since it was known to be highly selective toward terminal functionalization . The methoxycarbonylation offers an alternative to hydrosilylation to prepare such a methyl-ester-functionalized silsesquioxane.…”

Section: Carbonylation Reactions With 12-dtbpmbmentioning

confidence: 99%

Section: Carbonylation Reactions With 12-dtbpmbmentioning

confidence: 99%

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Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Vondran

Furst

Eastham³

et al. 2021

Chem. Rev.

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The bidentate phosphine ligand 1,2-bis(di-tert-butylphosphinomethyl)benzene (1,2-DTBPMB) has been reported over the years as being one of, if not the, best ligands for achieving the alkoxycarbonylation of various unsaturated compounds. Bonded to palladium, the ligand provides the basis for the first step in the commercial (Alpha) production of methyl methacrylate as well as very high selectivity to linear esters and acids from terminal or internal double bonds. The present review is an overview covering the literature dealing with the 1,2-DTBPMB ligand: from its first reference, its catalysis, including the alkoxycarbonylation reaction and its mechanism, its isomerization abilities including the highly selective isomerizing methoxycarbonylation, other reactions such as cross-coupling, recycling approaches, and the development of improved, modified ligands, in which some tert-butyl ligands are replaced by 2-pyridyl moieties and which show exceptional rates for carbonylation reactions at low temperatures.

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“…This stable cubic structure can be modified by adding different types of organic functional groups to the Si corners via suitable chemical reactions, and thus a variety of hybrid materials can be achieved. [3][4][5][6][7][8][9][10][11][12][13][14][15] Due to the unique characteristics of POSS, it has been used as a core to develop organic-inorganic hybrid liquid crystalline materials. The first octameric silsesquioxane-containing liquid crystal (LC) was reported in 1991, 16 after which a number of POSS-based LCs were generated by introducing different mesogens in the corner chains.…”

Section: Introductionmentioning

confidence: 99%

Organic–inorganic hybrid liquid crystals derived from octameric silsesquioxanes. Effect of the peripheral groups in mesogens on the formation of liquid crystals

et al. 2011

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Synthesis and crystal structures of bromo- and ester-functionalised polyhedral silsesquioxanes

Cited by 16 publications

References 20 publications

Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Organic–inorganic hybrid liquid crystals derived from octameric silsesquioxanes. Effect of the peripheral groups in mesogens on the formation of liquid crystals

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Synthesis and crystal structures of bromo- and ester-functionalised polyhedral silsesquioxanes

Cited by 16 publications

References 20 publications

Stochastic/Controlled Symmetry Breaking of the T8‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Stochastic/Controlled Symmetry Breaking of the T8‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Organic–inorganic hybrid liquid crystals derived from octameric silsesquioxanes. Effect of the peripheral groups in mesogens on the formation of liquid crystals

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Product

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Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Stochastic/Controlled Symmetry Breaking of the T₈‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks