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  • 1
    Electronic Resource
    Electronic Resource
    Small and Medium Rings, 75. Syntheses, Photoelectron Spectra, and Photoreactivity of Polycyclic 1,5-Diketones: Transannular Interaction in the Cyclooctane-1,5-dione Fragment (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 803-813 
    Details
    ISSN: 0009-2940
    Keywords: PE spectroscopy ; Lone-pair interaction ; Orbitals, localized ; Orbitals, precanonical ; 1,5-Diketones, polycyclic ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five polycyclic 1,5-diketones 1 - 4 and 6 are synthesized and studied by means of He(Iα) PE spectroscopy. Comparison of the spectra indicates significant differences in Orbital Interaction Through Bond, which is explained by computational methods, especially by analyses of the precanonical MOs. The lone pair splitting observed in diketone 1, ΔI(n)=0.75 eV, seems to be the largest one ever found in a 1,5-diketone, obviously due to a favourable zigzag topology of the σ frame. In addition, coupling reactions and photoreactivity are studied in compound 6, which seemed to be well suited for Orbital Interaction Through Space. The crystal structure of 6 and its photoproduct 21 is solved by X-ray crystallography.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240421
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  • 2
    Electronic Resource
    Electronic Resource
    Small and Medium Rings, 74. Syntheses and Photoelectron Spectra of 7-Azanorbornadiene and Related Compounds An Analysis with Fragment Orbitals (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 791-801 
    Details
    ISSN: 0009-2940
    Keywords: Lone-pair orientation ; Lone pair interaction ; Precanonical orbitals ; Orbitals, localized ; Calculations, ab initio STO-3G, MNDO, MM2 force field ; PE Spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The He(I) photoelectron spectra (PE) of 7-azanorbornane (5), 7-azanorbornene (6), and 7-azanorbornadiene (7) as well as of related urethanes have been recorded. The syntheses of these bicyclic compounds are described in detail. A most convenient analysis of the PE spectroscopic results is based on the procedure of Heilbronner-Schmelzer on an ab initio STO-3G level. This method allows to construct fragment orbitals elucidating the orientation of the nitrogen lone pair, the through-space interaction with π bonds, and the participation of σ bond orbitals. The result is remarkable: whereas the direct interaction of localized lone-pair and π orbitals is significant in both syn;- and anti-orientation, the interaction of a localized lone pair with a precanonical fragment π orbital is completely different in the two geometries. In 6;-syn a considerable interaction matrix element FantiΨnπ=-0.71 eV comes to the fore, whereas the corresponding parameter in 6;-anti turns out to be almost zero, FantiΨnπ=+ 0.09 eV. Since 6;-syn is calculated to be more stable than 6;-anti, it is this invertomer, 6;-syn, which is likely to be responsible for the main bands in the PE spectrum of 6. The comparatively large experimental split between the first two PE bands of 6 (0.98 eV) is in accord with the 6;-syn geometry and compares well with the calculated band separation of 1.26 eV for 6;-syn.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240420
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  • 3
    Electronic Resource
    Electronic Resource
    Vinylogous β-Carotenes: Generation, Storage, and Delocalization of Charge in Carotenoids (1997)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 2205-2213 
    Details
    ISSN: 0947-3440
    Keywords: Carotenoids ; C26—C70 β-carotenes ; Cyclic voltammetry ; Photoelectron spectroscopy ; Semiempirical calculations ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, we report on the synthesis of β-carotenes of variable chain length with between 5 and 23 double bonds (1-7). These oligoenes were prepared by McMurry and Wittig reactions. The tetradecapreno-β-carotene 7 would seem to be the longest β-carotene yet reported. Furthermore, we investigated the electronic properties using cyclic voltammetry and photoelectron spectroscopy (UPS) to generate open-shell and closed-shell ions of carotenoids in solution and in the solid state, respectively. With increasing chain length (≥ 11 double bonds), even the generation of tetracations and tetraanions could be observed by cyclic voltammetry. Extending the number of conjugated bonds causes the potentials to converge to limiting values. All electron-transfer processes occur in one-electron steps, which are close to each other in pairs. The potential difference between the first oxidation potential and the first reduction potential is a linear function of the reciprocal chain length. Despite the different techniques used (CV and UPS) and the different condensed phases, there is an excellent correspondence between the energies of the radical cation states generated by the two methods. This shows that the radical cation formation is principally determined by the chain length. The structures of the ion states were investigated using semiempirical methods at the NDDO level. Charge delocalization and bond relaxation are not identical and do not utilize the same number or the same kind of atoms. It can be shown that from the length of 20 double bonds onwards, the effective conjugation length for doubly-charged cations converges slowly to a limiting value.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.199719971106
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  • 4
    Electronic Resource
    Electronic Resource
    Proximity Effects in Organic Chemistry - The Photoelectron Spectroscopic Investigation of Non-Bonding and Transannular InteractionsBecause the term neighboring group participation is reserved for “through space” interactions between substituent and reaction center [19], all interactions between non-neighboring groups or orbitals (distance ≥ 1,3) are designated as proximity effects in this article, irrespective of whether they are “through space” or “through bond” in nature. (1983)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 22 (1983), S. 283-314 
    Details
    ISSN: 0570-0833
    Keywords: Proximity effects ; Transannular interactions ; Photoelectron spectroscopy ; Noncovalent interactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical structural formulas often convey the impression only those relationships between the atoms are of importance which hold a molecule together as symbolized by the chemical bonds. However, many interactions between atoms or groups of atoms are not adequately denoted in this manner. Nevertheless, their existence can have important consequences for ground state energies (cis-difluoroethylene is more stable than trans-difluoroethylene), conformations (the syn form of methyl vinyl ether is more stable than the anti form), reactivities (an endo cyclopropane ring in 7-anti-norbornyl derivatives accelerates solvolysis by a factor of 1014), UV spectra (“superposition” of the π-systems of acridine and purine-bonded through a four-membered chain-results in hypochromism), CD spectra (the inherently symmetrical but dissymmetrically perturbed chromophore of 2-deuterionorbornadiene allows the observation of three transitions in the near UV), and ESR spectra (the long-range coupling with H-4 in the bridgehead bicyclo[2.1.1]hex-1-yl radical equals 22.5 G). Since orbital interactions are involved in most intramolecular effects of this kind, photoelectron spectroscopy has proven an informative and valuable extension to other methods.
    Additional Material: 37 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198302831
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