Topic
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: An X-ray crystallographic study of a rhodium hydride complex containing a cis-chelating diphosphine, isolated from the reaction of a cationic Rhodium(I) hydrogenation catalyst precursor [Rh(dipp)(nbd)]ClO4[dipp = Pri2PC3H6PPri2, nbd = norbornadiene] with H2, has revealed the structure as [{Rh(Dipp)H}2(µ-H)2 (µ)-ClO 4] as mentioned in this paper.
Abstract: An X-ray crystallographic study of a rhodium hydride complex containing a cis-chelating diphosphine, isolated from the reaction of a cationic rhodium(I) hydrogenation catalyst precursor [Rh(dipp)(nbd)]ClO4[dipp = Pri2PC3H6PPri2, nbd = norbornadiene] with H2, has revealed the structure as [{Rh(dipp)H}2(µ-H)2(µ-ClO4)]ClO4, suggesting the presence of a rhodium cis-dihydride species [Rh(dipp)(H)2S2]+(S = solvent), as an intermediate.
6 citations
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TL;DR: In this article, it was shown that 2-(MeR 1 CCR 2 )-pyridine undergoes a 1,3-double-bond shift on displacement of norbornadiene from [M(CO) 4 norb] (M = Cr, Mo or W) to give complexes of the type [M[CO] 4 LL'] (LL' = 2-(allyl)or 2-(substituted allyl)-Pyridine), which do not exhibit conformational isomerism involving the plane of the coordinated o
6 citations
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TL;DR: In this article, the photochemical valence isomerization of pendant norbornadiene (NBD) to quadricyclane (QC) moieties occurred in films upon irradiation with 365 nm light NBD polyimide (P-1a) prepared from hex afluoroisopropylidene-2-bis(phthalic anhydride) and 2,2 -bis(3-amino-4-methylphenyl)hexafluoropropane showed a higher photochemical reactivity than the other N
Abstract: Polymers having pendant norbornadiene (NBD) moieties and rigid main chains were prepared from reactions in DMF of pendant bromomethyl groups present in polyimides with a potassium carboxylate or phenolate derivatives of NBD using a phase transfer catalyst The substitution was quantitative using tetrabutylammonium bromide at room temperature The photochemical valence isomerization of pendant NBD to quadricyclane (QC) moieties occurred in films upon irradiation with 365 nm light NBD polyimide (P-1a) prepared from hex afluoroisopropylidene-2-bis(phthalic anhydride) and 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane showed a higher photochemical reactivity than the other NBD polyimides when the polymers were irradiated with 365 nm light While usual polyimides have absorptions around 365 nm that hinder the photo-isomerization of NBD and also cause the polymer to decompose because of the irradiation, the P-1a matrix has no absorption at wavelengths above 340 nm and irradiation hardly affected the rate of isomerization When the irradiated NBD polymers were heated, the reversion isomerization of the QC moieties to the original NBD moieties occurred easily concurrent with their decomposition The rigid polyimide structure stabilizes the QC moieties and protects them from degradation during cyclic isomerization between NBD and QC For example, the half-life of a pendant QC moiety in a polyimide is estimated to be 6 years at 25°C
6 citations
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TL;DR: The transition-metal complexes were characterized by multinuclear NMR spectroscopy, mass spectrometry, infrared spectroscopic, and X-ray crystallography and the mechanism of the rearrangement was supported by quantum-mechanical calculations.
Abstract: 1,3,5-Triphospha-1,4-pentadiene-2,4-diamine reacts with [M(CO)4L] (M = Mo, L = nbd (norbornadiene); M = W, L = 2 CH3CN) to give the chelate complexes [M(CO)4(PMes{C(NHCy)PMes}2-κ P1 ,P3)]. In contrast, an unusual intramolecular rearrangement occurred with [Cu(CH3CN)4]PF6 leading to the dimeric copper(I) complex [Cu(CNCy){PHMesPMesC(NHCy)PMes-κ P1 ,P3}]2(PF6)2. The mechanism of the rearrangement was supported by quantum-mechanical calculations. The transition-metal complexes were characterized by multinuclear NMR spectroscopy, mass spectrometry, infrared spectroscopy, and X-ray crystallography.
6 citations
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TL;DR: In this paper, new cage lactones were synthesized by photocyclization of tricyclodienolactones 1a, 1b, 2 which were available from the Diels-Alder reactions of 2-pyrones with p-benzoquinones or norbornadiene.
6 citations