1,3-Pentadiene

Zhong, Hua; Rawal, Viresh H.

doi:10.1002/047084289x.rp024

Cited by 2 publications

(2 citation statements)

References 67 publications

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“…The structure of one of the enantiomers is depicted in Figure 1 and is very different from the Mtrop compounds. The Rh(I)(cod) fragment binds to C1, C2, C3, C4 and C5 at distances between 2.09 to 2.40 Å (see legend to Figure 1 ) of the central seven-membered ring in a way which is also observed in other metal [ 43 , 44 ] and specifically, Rh(I) pentadienide complexes [ 43 , 44 ]. This pentadienide-type interaction donates 6π electrons to the Rh(I)(cod) fragment which thereby reaches an 18-electron configuration.…”

Section: Resultsmentioning

confidence: 67%

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings

et al. 2020

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The synthesis, isolation and full characterization of ion pairs between alkaline metal ions (Li+, Na+, K+) and mono-anions and dianions obtained from 5H-dibenzo[a,d]cycloheptenyl (C15H11 = trop) is reported. According to Nuclear Magnetic Resonance (NMR) spectroscopy, single crystal X-ray analysis and Density Functional Theory (DFT) calculations, the trop‒ and trop2−• anions show anti-aromatic properties which are dependent on the counter cation M+ and solvent molecules serving as co-ligands. For comparison, the disodium and dipotassium salt of the dianion of dibenzo[a,e]cyclooctatetraene (C16H12 = dbcot) were prepared, which show classical aromatic character. A d8-Rh(I) complex of trop− was prepared and the structure shows a distortion of the C15H11 ligand into a conjugated 10π -benzo pentadienide unit—to which the Rh(I) center is coordinated—and an aromatic 6π electron benzo group which is non-coordinated. Electron transfer reactions between neutral and anionic trop and dbcot species show that the anti-aromatic compounds obtained from trop are significantly stronger reductants.

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Section: Resultsmentioning

confidence: 67%

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings

et al. 2020

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“…The results of the distortion/interaction analysis for the reactions of benzyne with cis -pentadiene are shown at the right side of Figure , and the corresponding transition structures are shown at the bottom of Figure . The distortion energies for the concerted [4 + 2] reaction are much higher than that for the trans system seemingly because of steric repulsion between the methyl group and the alkene in the s- cis conformation . The [4 + 2] transition structure is later, which accentuates the distortion.…”

Section: Resultsmentioning

confidence: 99%

Mechanism and the Origins of Periselectivity in Cycloaddition Reactions of Benzyne with Dienes

Hashimoto

Tantillo

2022

J. Org. Chem.

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Density functional theory calculations have been used to explore the reaction mechanism of (4 + 2) and (2 + 2) cycloadditions of benzyne with classical dienes. The results indicate the following: (1) (4 + 2) products arise via concerted pathways, (2) (2 + 2) products arise via stepwise pathways with diradical intermediates, and (3) these diradical intermediates are formed via isomerization of carbene intermediates. The origins of periselectivity in these reactions are analyzed using distortion/interaction analysis for the key steps, and they indicate that the tiny distortion in the very early [4 + 2] transition structure, coupled with an entropic favorability, controls selective (4 + 2) cycloaddition.

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1,3-Pentadiene

Cited by 2 publications

References 67 publications

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings

Mechanism and the Origins of Periselectivity in Cycloaddition Reactions of Benzyne with Dienes

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