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Norbornadiene
About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.
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TL;DR: In this article, a trichlorosilane was used to hydrosilylate norbornene in the presence of palladium catalyst (0.01-0.1 mol %) coordinated with ( R )-MOP ligand, which was oxidized with hydrogen peroxide to give (1 S,2 S,4 R ) -exo -2-norbornanol in 96% ee.
95 citations
TL;DR: In this paper, the photoreactivity is correlated with the surface lattice oxygen, and a mechanism is proposed to explain the photoisomerization and role of Fe dopant.
Abstract: Metal(V, Fe, Ce, Cu, Cr)-doped TiO2 were synthesized for the photoisomerization of norbornadiene. Characterizations indicate that V and Fe are located in the substitutional sites of TiO2, Ce ions dispersed in the interstitial sites, while Cr and Cu aggregated on the surface. The order of activity is Fe−TiO2 > V−TiO2 > Cr−TiO2 > Ce−TiO2 > TiO2 > Cu−TiO2, suggesting the local structure and type of dopant are crucial. Materials with various V and Fe content were further studied. Fe ions are well dispersed in TiO2 lattice even at high metal content, whereas many separated V2O5 phases are formed. The activity of V−TiO2 changes with V content and the optimal Ti/V ratio is 15, but the activity of Fe−TiO2 is independent of the metal content. Attributed to the high dispersion, Fe−TiO2 is much more active than V−TiO2. The photoreactivity is correlated with the surface lattice oxygen, and a mechanism is proposed to explain the photoisomerization and role of Fe dopant.
95 citations
TL;DR: The synthesis, characterization, and computational evaluation of a series of low molecular weight norbornadiene–quadricyclane systems indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.
Abstract: Molecular solar-thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193-260 g mol(-1)) norbornadiene-quadricyclane systems. The molecules feature cyano acceptor and ethynyl-substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo-thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396-629 kJ kg(-1)). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.
94 citations
TL;DR: In this article, the authors used a [Rh(norbornadiene)Cl]2 catalyst in the presence of triethylamine to give poly((o-ethoxyphenyl)acetylene) (POEPA) bearing a cis-transoid form under mild conditions.
Abstract: Stereoregular polymerization of (o-ethoxyphenyl)acetylenes (OEPA) was performed using a [Rh(norbornadiene)Cl]2 catalyst in the presence of triethylamine to give poly((o-ethoxyphenyl)acetylene) (POEPA) bearing a cis-transoid form under mild conditions. The polymer underwent isomerization from the predominant cis form to the trans form when compressed at 200 kg/cm2 at room temperature. The polymers, obtained before and after the compression, were characterized in detail using laser Raman, diffuse reflective UV, ESR, and X-ray diffraction. The data suggested that the isomerization of the resulting polymer from the cis-transoid to the trans-transoid form was induced to give rise to the conjugated trans-planar zigzag structures, where unpaired electrons are stabilized as mobile electrons called solitons. The formation of the soliton radicals was confirmed by the motional narrowing of the line width observed in the ESR spectra of the compressed polymer. The trans conjugation length, n, (CC)n generated by the co...
94 citations
TL;DR: A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.
Abstract: The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 °C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73−95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 4...
93 citations