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: The photoelectron spectra of quadricyclane (3) and 3-methylidene (4) have been measured and the results served as a basis for the elucidation of the electronic structure of these compounds, which agreed with theoretical calculations as discussed by the authors.
Abstract: The photoelectron spectra of quadricyclane (3) and 3-methylidene quadricyclane (4) have been measured. The results served as a basis for the elucidation of the electronic structure of these compounds, which agreed with theoretical calculations. It is found that the symmetry of the HOMO of 3 is different when compared to that of its valence isomer norbornadiene (1). The results also indicate that the structure of the highest occupied orbitals cannot be derived by only considering the Walsh-orbitals of the two three-membered rings. In addition one of the Walsh-components of the four-memebered ring has to be taken into account.
32 citations
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TL;DR: In this paper, the combination of polyethylene (PE) matrices and high pressure−low temperature (HPLT) experiments can be used to provide new mechanistic information on hydrogenation processes.
Abstract: This paper presents a new method for investigating the mechanisms of homogeneously catalyzed reactions involving gases, particularly H2. We show how the combination of polyethylene (PE) matrices and high pressure−low temperature (HPLT) experiments can be used to provide new mechanistic information on hydrogenation processes. In particular, we show how we are able to generate reaction intermediates at low temperature, and then to extract the contents of the PE film at room temperature to characterize the organic products using GC-MS. We have used our new technique to probe both the hydrogenation of dimethyl fumarate (DF), using Fe(CO)4(η2-DF) as the catalytic species, and the hydrogenation of norbornadiene (NBD), using (NBD)M(CO)4 (M = Cr or Mo) as the catalytic species. Irradiation of Fe(CO)4(η2-DF) in a PE matrix at 150 K resulted in the formation of an intermediate complex tentatively assigned Fe(CO)3(η4-DF). Warming this complex to 260 K under H2 leads to the formation of Fe(CO)3(η2-DF)(η2-H2). Further...
32 citations
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TL;DR: In this paper, a DFT study showed that the different behavior of py and stronger π-acceptor ligands, as CO and PR3 toward 1, has been explained through the DFT analysis.
32 citations
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TL;DR: A new phosphine-free palladacycle catalyst 4 was prepared from benzyl oxazoline in high yield and fully characterized, and hydrophenylation reactions of a wide range of bicyclic alkenes, not only norbornene and norbornadiene but also oxa- and aza-bicyclic al Kenes proceeded smoothly under aerobic condition without exclusion of water.
Abstract: A new phosphine-free palladacycle catalyst 4 was prepared from benzyl oxazoline in high yield and fully characterized. With it as catalyst, hydrophenylation reactions of a wide range of bicyclic alkenes, not only norbornene and norbornadiene but also oxa- and aza-bicyclic alkenes, with iodobenzene proceeded smoothly under aerobic condition without exclusion of water. Up to 1.7 x 10(6) TON as well as 1.2 x 10(5) TOF were achieved.
31 citations
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TL;DR: In this paper, the exo-trans-exo configuration of a mixture of benzonorbornadiene with enneacarbonyldiiron, Fe2(CO)9, at room temperature gave tetracarbonyl(l, 4-dihydro-1,4-epoxynaphthalene)iron, in which the olefinic δ-bond is bonded to the metal.
Abstract: Reaction of benzonorbornadiene, 7-isopropylidenebenzonorbornadiene (1,4-dihydro-9-isopropylidene-1,4-methanonaphthalene) and 1,4-dihydro-1,4-epoxynaphthalene (7-oxabenzonorbornadiene) with dicarbonyldinitrosyliron, Fe(CO)2(NO)2, gave in good yields the corresponding dimers having the exo-trans-exo configuration. Treatment of a mixture of benzonorbornadiene and norbornadiene with Fe(CO)2(NO)2 gave a 'crossed dimer', in addition to the dimers derived from benzonorbornadiene and norbornadiene. The reaction of benzonorbornadiene with pentacarbonyliron at 100o gave the exo-trans-exo dimer and a ketone derived by dimerization and carbonyl insertion. This ketone, and the analogous ketone obtained from 7-isopropylidenebenzonorbornadiene, have been assigned the exo-trans-exo configuration. Reaction of 1,4-dihydro-1,4-epoxynaphthalene with enneacarbonyldiiron, Fe2(CO)9, at room temperature gave tetracarbonyl(l,4-dihydro-l,4-epoxynaphthalene)iron(0), in which the olefinic ח-bond is bonded to the metal. In solution at 63o this complex gave naphthalene.
31 citations