TY - JOUR
A1 - Homann, Arne
A1 - Qamar, Riaz-ul
A1 - Serim, Sevnur
A1 - Dersch, Petra
A1 - Seibel, Juergen
T1 - Bioorthogonal metabolic glycoengineering of human larynx carcinoma (HEp-2) cells targeting sialic acid
N2 - Sialic acids are located at the termini of mammalian cell-surface glycostructures, which participate in essential interaction processes including adhesion of pathogens prior to infection and immunogenicity. Here we present the synthesis and bioorthogonal metabolic incorporation of the sialic acid analogue N-(1-oxohex-5-ynyl)neuraminic acid (Neu5Hex) into the cell-surface glycocalyx of a human larynx carcinoma cell line (HEp-2) and its fluorescence labelling by click chemistry.
KW - Organische Chemie
KW - bioorthogonal metabolic glycoengineering; click chemistry; sialic acid
Y1 - 2010
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-67806
ER -
TY - JOUR
A1 - Pratihar, Pampa
A1 - Ghosh, Suhrit
A1 - Stepanenko, Vladimir
A1 - Patwardhan, Sameer
A1 - Grozema, Ferdinand C.
A1 - Siebbeles, Laurens D. A.
A1 - Würthner, Frank
T1 - Self-assembly and semiconductivity of an oligothiophene supergelator
N2 - A bis(trialkoxybenzamide)-functionalized quaterthiophene derivative was synthesized and its self-assembly properties in solution were studied. In non-polar solvents such as cyclohexane, this quaterthiophene π-system formed fibril aggregates with an H-type molecular arrangement due to synergistic effect of hydrogen bonding and π-stacking. The self-assembled fibres were found to gelate numerous organic solvents of diverse polarity. The charge transport ability of such elongated fibres of quaterthiophene π-system was explored by the pulse radiolysis time resolved microwave conductivity (PR-TRMC) technique and moderate mobility values were obtained. Furthermore, initial AFM and UV-vis spectroscopic studies of a mixture of our electron-rich quaterthiophene derivative with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) revealed a nanoscale segregated assembly of the individual building blocks in the blend.
KW - Organische Chemie
KW - charge transport; hydrogen bonding; oligothiophene; organogel; self-assembly
Y1 - 2010
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-67817
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Türk, M.
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Octahydro-1,2,3:4,5,6-dimethenopentalen-2-carbonitril, das erste Derivat eines noch unbekannten (CH)\(_{10}\)-Kohlenwasserstoffs
N2 - No abstract available
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58728
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Türk, M.
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Octahydro-1,2,3:4,5,6-dimethenopentalene-2-carbonitrile, the First Derivative of a Yet-Unknown (CH)\(_{10}\)-Hydrocarbon
N2 - No abstract available
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58731
ER -
TY - JOUR
A1 - Bentley, T. W.
A1 - Christl, Manfred
A1 - Kemmer, R.
A1 - Llewellyn, G.
A1 - Oakley, J. E.
T1 - Kinetic and Spectroscopic Characterisation of Highly Reactive Methanesulfonates. Leaving Group Effects for Solvolyses and Comments on Geminal Electronic Effects Influencing S\(_N\)1 Reactivity
N2 - Highly reactive methanesulfonates (mesylates, ROMs) have been prepared from 1-phenylethanol. cyclohex-2-en-1-ol, diphenylmethanol and p-methoxybenzyl alcohol by treatment with methanesulfonyl chloride and triethylamine in dichloro- or trichloro-methane at - 20 to 0 °C. The mesylates. characterised in solution by \(^1\)H and \(^{13}\)C NMR at -20 °C, were obtained in satisfactory purity (ca. 95%) in cold solutions but they decomposed by reaction with chloride, triethylamine or the parent alcohol. Rate constants for solvolyses in aqueous acetone and aqueous ethanol have been determined by a fast response conductimetric method. Product selectivities for solvolyses of pmethoxybenzyl mesylate in aqueous ethanol and methanol at 0 °C have been determined by HPLC. From additional new or Iiterature kinetic data for solvolyses of corresponding bromides. chlorides and p-nitrobenzoates (OPNB). Br/CI. OMs/Br and OMs/OPNB rate ratios were calculated; the results are consistent with electronic effects stabilising the carbocationic transition states and increasing OMs/Br rate ratios for these SN 1 solvolyses; none of the evidence supports a geminal electronic effect on Br/CI rate ratios (e.g. caused by stabilisation of the initial state in pmethoxybenzyl chloride). Steric effects on ester /halide rate ratios for solvolyses of tertiary substrates are confirmed. Relative rates over a 10\(^{16}\) range for ester and halide leaving groups are evaluated for solvolyses of 1-phenylethyl substrates in 80% ethanol-water. updating previous work by Noyce et al. (1972).
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58748
ER -
TY - JOUR
A1 - Suter, H. U.
A1 - Pleß, V.
A1 - Ernzerhof, M.
A1 - Engels, Bernd
T1 - Difficulties in the Calculation of Electron Spin Resonance Parameters using Density Functional Methods
N2 - Density functional theory is applied to the calculation ofthe isotropic byperfine coupJing constants in some small molecules. Various functionals are tested. The agreement of the calculated values to experimental data and values obtained from sophisticated ab initio methods depends on the functionals used and the system under consideration. With respect to spin density calculations the functional of Lee, Yang and Parr with Becke's excbange functional (BLYP) is found to give good results for tbe heavier center of the CH and the NH molecule, while the spin densities of other molecules such as OH, H\(_2\)CN, H\(_2\)CO\(^+\), NO and O\(_2\) deviate considerably from experimental and/or other theoretical results (30%-60%). In cases where the singly occupied orbital can contribute to the isotropic hyperfine coupling constants, accurate results are obtained. The reason fortbis is analyzed.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59113
ER -
TY - JOUR
A1 - Mühlhäuser, M.
A1 - Froudakis, G.
A1 - Zdetsis, A.
A1 - Engels, Bernd
A1 - Flytzanis, N.
A1 - Peyerimhoff, S. D.
T1 - Ab initio investigation of the stability of Si\(_3\)C<\(_3\) clusters and their structural and bonding features
N2 - Various structural possibilities for Si\(_3\)C\(_3\) clusters are investigated by ab initio calculations employing basis sets of double- and triple-zeta quality augmented by d polarization functions. Correlation effects are included by a second-order Moeller Piesset perturbation treatment. For the two lowest-lying structures higher-order correlation corrections and multi-reference effects are also included. Bonding features are investigated by two different types of population analyses to obtain insight into the nature of chemical bonding. A total of 17 stationary points were investigated, 14 of which correspond to local minima and three being transition states. The energetically lowest-lying structures are: A "pyramidlike" structure with various multicenter bonds, followed by a es symmetric isomer closely related to the ground state Si6 structure. Planar structures, favoured in small carbon clusters, lie higher in energy and are transition states. The lowest-lying triplet system is found to be the linear nonsymmetric Si - C-C-C-Si -Si structure, which is calculated to lie about 38 kcalfmole above the singlet ground state. A building-up principle based on bonding criteria is suggested for the occurence of the various structural possibilities.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59060
ER -
TY - JOUR
A1 - Wortmann-Saleh, D.
A1 - Engels, Bernd
A1 - Peyerimhoff, S. D.
T1 - Theoretical Study of the Reaction O(\(^3\)P) + C\(_2\)H\(_4\) and comparison with the \(^3\)CH\(_3\) + C\(_2\)H\(_4\) Reaction
N2 - The minimum energy path for the reaction O(\(^3\)P\(_g\)) + C\(_2\)H\(_4\)(\(^1\)A\(_g\)) has been calculated by optimizing all relevant geometrical parameters along the approach of oxygen to ethene. A barrier of 4.7 kcal/mol in the \(^3\)A"( ... 9a'\(^2\)- 10a'3a") potential energy surface and an energy difference of 14.4 kcal/mol between the product and the fragments is found at the multireference-configuration interaction level. The corresponding values at the lower-level treatment CASSCF are 9 kcal/mol for the barrier and 9 kcal/mol for the depth of the potential; this shows the importance of inclusion of electron correlation. The barrier for CH\(_2\) rotation for the lowestenergy structure (asymmetric OC\(_2\)H\(_4\)) is around 5 kcal/mol. The energy gap to the first excited state \(^3\)A'( ... 9a'l0a'3a'12) is found tobe 3.6 kcal/mol in MRD-CI calculations at the ground-state minimum. Comparison with \(^3\)CH\(_2\) + C\(_2\)H\(_4\) shows that in this system the lowest-energy surface is \(^3\)A', i.e., the state which is the excited state in 0 + C\(_2\)H\(_4\). This difference in energy ordering of \(^3\)A' and \(^3\)A" states results from the fact that the p\(_x\), p\(_y\), p\(_z\) degeneracy of oxygen orbitals is lifted in \(^3\)CH\(_2\)leading to b\(_1\), b\(_2\). and a\(_1\) MOs whereby the lowest b\(_2\) (a") remains doubly occupied; as a consequence, the reaction pattem between the oxygen and \(^3\)CH\(_2\) approach is different, which is also quite apparent in the calculated charge transfer.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59076
ER -
TY - JOUR
A1 - Staikova, M.
A1 - Peric, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S. D.
T1 - Ab initio Investigation of the Structure of the X\(^2\)A', A\(^2\)A'' (1\(^2\)Π) Spectral System of HCO: Investigation of the Magnetic Hyperfine Effects
N2 - Results ofan ab initio study ofthe hyperfine structure of the X\(^2\)A', A\(^2\) A" ( 1\(^2 \Pi\)) system ofthe formyl radical are presented. Special attention is paid to the analysis of the interplay between the vibronic and magnetic hyperfine etfects. The results of computations are in very good agreement with the available experimental findings. The values for the hyperfine coupling constants in lower bending Ievels of both electronic species are predicted.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59089
ER -
TY - JOUR
A1 - Froudakis, G.
A1 - Zdetsis, A.
A1 - Mühlhäuser, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S. D.
T1 - A comparative ab initio study of the Si\(_2\)C\(_4\), Si\(_3\)C\(_3\), Si\(_4\)C\(_2\) clusters
N2 - Various structural possibilities for the Si\(_2\)C\(_4\) and Si\(_4\)C\(_2\) clusters are investigated by employing a basis set of triple-zeta plus polarization quality; electron correlation is generally accounted for by second-order M0ller-Plesset and, in certain instances, by higher-order perturbation (CASPT2) approaches. The building-up principle recently suggested from an analysis of Si\(_3\)C\(_3\) clusters is found to be fully operative for Si\(_2\)C\(_4\) and Si\(_4\)C\(_2\) clusters. A comparison of the structure and stability of various geometrical arrangements in the series C\(_6\) , Si\(_2\)C\(_4\) , Si\(_3\)C\(_3\) , Si\(_4\)C\(_2\), and Si\(_6\) shows that linear and planar structures become rapidly less stable if carbons are replaced by silicons and that the three-dimensional bipyramidal forms become less favorable as soon as silicons are exchanged by carbons in the parent Si\(_6\) structure. The effects can be rationalized in qualitative terms based on differences in silicon and carbon bonding.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59097
ER -
TY - JOUR
A1 - Suter, H. U.
A1 - Huang, M.-B.
A1 - Engels, Bernd
T1 - A Multireference Configuration Interaction Study of the Hyperfine Structure of the Molecules CCO, CNN and NCN in their triplet ground states
N2 - The hyperfine structures of the isoelectronic molecules CCO. CNN, and NCN in their triplet ground states (X\(^3 \sum ^-\)) are investigated by means of ab initio methods. The infrared frequencies and geometries are detennined and compared with experiment. Configuration selected multireference configuration interaction calculations in combination with perturbation theory to correct the wave function (MRD-CI/B\(_K\)) employing extended atomic orbital (AO) basis sets yielded very accurate hyperfine properties. The theoretical values for CCO are in excellent agreement with the experimental values determined by Smith and Weltner [J. Chem. Phys. 62,4592 (1975)]. For CNN, the first assignment of Smith and Weltner for the two nitrogen atoms has to be changed. A qualitative discussion of the electronic structure discloses no simple relation between the structure of the singly occupied orbitals and the measured hyperfine coupling constants. Vibrational effects were found to be of little importance.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59108
ER -
TY - JOUR
A1 - Staikova, M.
A1 - Engels, Bernd
A1 - Peric, M.
T1 - Ab initio investigation of the hyperfine structure in the 1\(^2\)Π\(_u\)(X\(^2\)A\(_1\), A\(^2\)B\(_1\) system of BH\(_2\))
N2 - No abstract available
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59000
ER -
TY - JOUR
A1 - Engels, Bernd
T1 - Detailed study of the configuration selected multi-reference configuration interaction method combined with perturbation theory to correct the wave function
N2 - A reliable prediction of the isotropic hyperfine coupling constant A\(_{iso}\) is still a difficult task for ab initio calculations. In previous studies, the configuration selected multireference configuration interaction method in combination with perturbation theory to correct the wave function (MRCI/ B\(_K\)) yielded accurate isotropic hyperfine coupling constants very economically. The present study gives a detailed analysis of the MRCI/ B\(_K\) method based on the X\(^2 \pi\) state of CH as a test case. Furthermore, a comparison to various other methods such as Maller-Ptesset perturbation theory and the coupled cluster approach is made. The success of the MRCI/ B\(_K\) method in predicting isotropic hyperfine coupling constants is explained in terms of the inßuence of higher than double excitations.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59019
ER -
TY - JOUR
A1 - Suter, H. U.
A1 - Engels, Bernd
T1 - Theoretical investigation of ESR parameters: H\(_2\)CN and H\(_2\)CO\(^+\)
N2 - The hyperfine structure of the two isoelectronic molecules H\(_2\)CN and H\(_2\)CO\(^+\) in their electronic ground state (X\(^2\)B\(_2\)) is studied. The influence of the atomic orbital (AO), basis sets, of the correlation treatment, and of the. equilibrium geometry on the obtained hyperfine propertles 1s - investigated. It is found that the multireference double excitation-configuration interaction (MRD-CI)/ BK treatment in which an MRD-CI wave function is corrected by a modified B\(_K\) method yields equivalent results to quadratic CI [QCISD(T)], coupled cluster single doubles [CCSD(T)), or Brueckner doubled [BD(T)]. Uncertainties in the equilibrium geometries are found to be the major source for discrepancies between theoretically and experimentally determined isotropic hyperfine coupling constants (hfccs). For the heavier centers, the calculated values of the isotropic hfccs agrees nearly perfectly with experimental values (\(\approx\) 1%-2%). The calculated values for the hydrogens are too low, but using the equilibrium structure suggested by Yamamoto and Sato [J. Chem. Phys. 96, 4157 ( 1992)], the best estimate deviates by less than 3%.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59029
ER -
TY - JOUR
A1 - Mühlhäuser, M.
A1 - Engels, Bernd
A1 - Marian, C. M.
A1 - Peyerimhoff, S. D.
A1 - Bruna, P. J.
A1 - Jansen, M.
T1 - Einfluß der Ladungsverteilung auf die Bindungslängen im P\(_4\)O\(_6\) Gerüst bei Verbindungen des Typs P\(_4\)O\(_6\)X
N2 - No abstract available
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59034
ER -
TY - JOUR
A1 - Huang, M.-B.
A1 - Suter, H. U.
A1 - Engels, Bernd
T1 - Theoretical Study of the Dimethylamino Radical (CH\(_3\))\(_2\)N and its protonated cation (CH\(_3\))\(_2\)NH\(^+\)
N2 - In the present work the dimethylamino radical ( ( CH\(_3\)) \(_2\)N) and its protonated cation ( ( CH\(_3\))\(_2\)NH\(^+\)) are investigated by means of ab initio methods. The geometries of various conformations of both compounds are obtained with UMP2/6·31 G** calculations, while the hyperfine structure and its dependence on the geometry is studied using the MRD-Cl/B\(_K\) method. The two molecules are compared to study the inftuence of the protonation on geometry and hyperfine structure. The effects of the rotational barriers on the hyperfine structures of (CH\(_3\))\(_2\)N, (CH\(_3\)CH\(_2\))\(_2\)N and ( (CH\(_3\))\(_2\)CH)\(_2\)N will be discussed.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59047
ER -
TY - JOUR
A1 - Pleß, V.
A1 - Suter, H. U.
A1 - Engels, Bernd
T1 - Ab initio study of the energy difference between the benzene and the cumulene form of the C\(_6\) molecule
N2 - The energy difference between the three lowest-lying isomers of C\(_6\) the linear \(^3 \sum ^-\) state and the two ring forms,the benzene structure (\(^1\)A\(_{18}\)) possessing D\(_{6h}\) symmetry and a distorted cyclic form ( \(^1\)A'\(_1\), D\(_{3h}\) symmetry) have been calculated using various ab initio methods. Variational methods such as multireference configuration interaction (MR-CI) and complete active space second order perturbatiOn treatment (CASPT2) have been applied, as weil as perturbational treatments and coupled cluster calculations (CCD). The correlation of all valence shell electrons is found to be important for a balanced description of the isomers of C\(_6\) . Methods which do not account for higher-order effects appropriately proved to be unsuitable for calculating the energy difference correctly. The results from multireference configuration interaction methods show that the isomers are close in energy with the cyclic forms somewhat lower than the linear form. The ring form possessing D\(_{3h}\) symmetry (\(^1\)A'\(_1\)} is found tobe the lowest-lying structure.
KW - Organische Chemie
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-59059
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Gerstner, E.
A1 - Kemmer, R.
A1 - Llewellyn, G.
A1 - Bentley, T. W.
T1 - Elektrophile Additionen an das Bicyclo[1.1.0]butan-System von 1-Phenyl- und 1-(4-Anisyl)tricyclo[4.1.0.0\(^{2,7}\)]heptan: Säure-katalysierte Reaktionen mit Wasser und Methanol, Anlagerung von Essigsäure und Oxymercurierung
N2 - No abstract available
KW - Organische Chemie
KW - 6-Norpinanols
KW - 6-aryl-
KW - preparation
KW - 6-Norpinyl 3
KW - 5-dinitrobenzoates
KW - hydrolysis
KW - Carbocations
KW - generation and rearrangement
KW - 2-Norcaranols
KW - 1-aryl-
KW - Cyclohept-3-en-1-ols
KW - 3-aryl-
KW - conformation
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58696
ER -
TY - JOUR
A1 - Gerstner, E.
A1 - Kemmer, R.
A1 - Christl, Manfred
T1 - Elektrophile Additionen an das Bicyclo[1.1.0]butan-System von Tricyclo[4.1.0.0\(^{2,7}\)]-heptan-Derivaten: Halogen-Elektrophile
T1 - Electrophilic Additions to the Bicyclo[l.l.O)butane System of Tricyclo[4.1.0.0\(^{2,7}\)]heptane Derivatives: Halogen Electrophiles
N2 - No abstract available
KW - Organische Chemie
KW - Norpinanes
KW - preparation
KW - Carbocations
KW - classical and nonclassical
KW - Neighbouring group participation
KW - Halonium ions
KW - Migratory aptitudes in carbocations
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58700
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Braun, Martin
A1 - Wolz, E.
A1 - Wagner, W.
T1 - Cycloallene, 9 - 1-Phenyl-1-aza-3,4-cyclohexadien, das erste Isodihydropyridin: Erzeugung und Abfangreaktionen
T1 - Cycloallenes, 9 - 1-Phenyl-1-aza-3,4-cyclohexadiene, the First Isodihydropyridine: Generation and Interception
N2 - No abstract available
KW - Organische Chemie
KW - Isoquinolines
KW - hexahydro-
KW - Cyclobuta[c}pyridines
KW - hexahydro-
KW - Cycloadditions
KW - [2 + 2]- and [4 + 2]-
KW - 3-Azabicyclo{3
KW - 1
KW - 0]hexane
KW - 6
KW - 6-dibromo-3-phenyl-
KW - 2
KW - 4-Pentadienylamine
KW - 3-n-butyl-N-phenyl-
Y1 - 1994
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58714
ER -
TY - JOUR
A1 - Metropoulos, B.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - On the chemi-ionization reaction O + CH ----> HCO\(^+\)+ e\(^-\). Coollinear O-CH Approach
N2 - We have investigated theoretically the importance of the O(\(^3\)P)+CH(a\(^4\sum^-\)) and the O(\(^3\)P)+CH(X\(^2\Pi\)) channels in the collinear chemi-ionization reaction O+CH->HCO\(^+\) +e\(^-\). We have found that both channels may lead to chemi-ionization via favorable Franck-Condon overlaps with the states ofthe ionic species.
KW - Organische Chemie
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58963
ER -
TY - JOUR
A1 - Engels, Bernd
T1 - Study of influences of various excitation classes on ab initio calculated isotropic hyperfine coupling constants
N2 - Reliable prediction of the isotropic hyperfine coupling constant A\(_{iso}\) is still a difficult task for ab initio calculations. Strang dependence on the method employed for its ca1culation has been found. Within a CI ansatz A\(_{iso}\) is considerably affected by the excitation classes taken into account within the CI calculation. In the present work the influence of various excitation classes on A\(_{iso}\) is examined. Calculations including all single, double, triple and a large part of the quadruple excitations are performed and the individual effects of the excitation classes are studied. It is found that the surprisingly good agreement found for S-CI treatments is due to large error cancellations. The importance of higher than double excitations arises from their indirect influence on the single excitations.
KW - Organische Chemie
KW - Spin density
KW - Hyperfine coupling constants
KW - Influence of excitation classes
KW - Indirect and direct contributions to Aiso
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58973
ER -
TY - JOUR
A1 - Gittins, C. M.
A1 - Harris, N. A.
A1 - Field, R. W.
A1 - Verges, J.
A1 - Ernst, W. E.
A1 - Bündgen, P.
A1 - Engels, Bernd
T1 - Analysis and Depertubation of the C\(^2\)Π and D\(^2\)Σ\(^+\) states of CaF
N2 - No abstract available
KW - Organische Chemie
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58980
ER -
TY - JOUR
A1 - Staikova, M.
A1 - Engels, Bernd
A1 - Peric, M.
A1 - Peyerimhoff, S. D.
T1 - Ab initio calculation of the vibronically averaged hyperfine coupling constants in the two lowest electronic states of H\(_2\)O\(^+\)
N2 - No abstract available
T2 - Ab initio calculations of the vibronically averaged hyperfine coupling constants in the 1\(^2\)Π\(_u\)(X\(^2\)B\(_1\),A\(^2\)A\(_1\)) state of the water cation
KW - Organische Chemie
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58998
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Lanzendörfer, U.
A1 - Grötsch, M. M.
A1 - Hegmann, J.
A1 - Ditterich, E.
A1 - Hüttner, G.
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Cycloadditionen von 6H-1,3,4-0xadiazin-6-onen (4,5-Diaza-α-pyronen), 12 - Dieckmann-Kondensationen ohne Basen
T1 - Cycloadditions of 6H-1,3,4-0xadiazin-6-ones (4,5-Diaza-α-pyrones), 12 - Dieckmann Condensations without Bases
N2 - No abstract available
KW - Organische Chemie
KW - 1
KW - 3
KW - 4-0xadiazine-2-carboxylate
KW - methyl 6-oxo-5-phenyl-
KW - Diels-Alder reactions
KW - Ketenes
KW - y-oxo-
KW - 1
KW - 2-Cyclopentanedione derivatives
KW - Adipic acid
KW - substituted 2-oxo- dimethyl esters
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58665
ER -
TY - JOUR
A1 - Feineis, E.
A1 - Schwarz, H.
A1 - Hegmann, J.
A1 - Christl, Manfred
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Cycloadditionen von 6H-1,3,4-0xadiazin-6-onen (4,5-Diaza-α-pyronen), 13 - Diels-Alder-Reaktionen mit 6H-1,3,4-Oxadiazin-6-onen als Dienophil
T1 - Cycloaddltions of 6H-1,3,4-0xadiazin-6-ones (4,5-Diaza-α-pyrones), 13 - Diels-Alder Reactions wtth 6H-1,3,4-0xadiazin-6-ones as Dienophile
N2 - No abstract available
KW - Organische Chemie
KW - 6H-1
KW - 3
KW - 4-0xadiazin-6-ones
KW - 1
KW - 2-Bismethylenecyclohexane
KW - Diels-Alder reactions
KW - [1
KW - 3
KW - 4]0xadiazino[4
KW - 5-b]isoquinolin-1-one derivatives
KW - Bicyclo[2.1.l]hexan-5-one
KW - highly substituted
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58673
ER -
TY - JOUR
A1 - Bentley, T. W.
A1 - Norman, S. J.
A1 - Gerstner, E.
A1 - Kemmer, R.
A1 - Christl, Manfred
T1 - Solvolysis of Tricyclo[3.1.0.0\(^{2,6}\)]hex-3-yl and Bicyclo[2.1.1]hex-2-yl Sulfonates
N2 - No abstract available
KW - Organische Chemie
KW - Bicyclo[1.1.0]butylcarbinyl sulfonates
KW - solvolysis of
KW - Cyclobutylcarbinyl sulfonates
KW - Anchimeric assistance in solvolysis
KW - Rearrangement of carbocations
KW - Electron demand in ditosylates
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58689
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Müller, H.
T1 - Induktiver Effekt, negative Hyperkonjugation und Gegenion sind nicht die Ursache der besonderen Eigenschaften des Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anions. - Eine NMR-Studie mit phenylsubstituierten Modellen
T1 - Inductive Effect, Negative Hyperconjugation, and Gegenion do not Cause the Unusual Properties of the Bicyclo[3.2.1]octa-3,6-dien-2-yl Anion. An NMR Study with Phenyl-Substituted Models
N2 - No abstract available
KW - Organische Chemie
KW - Tricyclo[3.3.1.0 2
KW - 4]non-7-en-6-ylpotassium
KW - 6-phenyl
KW - Homoaromaticity in carbanions
KW - Bicyclo[3.2.1]oct-3-en-2-yl anions
KW - phenyl-substituted
Y1 - 1993
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58655
ER -
TY - JOUR
A1 - Reuter, W.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - The Reaction of Singlet and Triplet Methylen with Ethene - A Multi-Reference CI Study
N2 - Large-scale multireference configuration interaction (MRD-CI) calculations in a flexible atomic orbital (AO) basis are employed to study the reaction of C\(_2\)H\(_4\) with CH\(_2\) in its firSt triplet and singlet state. The minimum energy path (MEP) of both reactions is calculated, and different mechanisms are discussed. To examine the possible participation of the singlet state in the overall reaction starting from the triplet channel and terminating in the singlet-state c-C\(_3\)H\(_6\), various cuts through both hypersurfaces are calculated. lt is found that favorable interconversion from the trip1et to the singlet surface can only occur at !arge separations of the two fragments of CH2 and C\(_2\)H\(_4\). Experimental data considering the vibrational motion of CH\(_2\) in connection with the relative position of both surfaces are used to obtain an estimate for the overall barrier of the reaction. The height of the barrier is about 6 kcal/mol, while the barrier of the pure triplet reaction is calculated to be 7-9 kcal/mol.
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58923
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peric, M.
A1 - Reuter, W.
A1 - Peyerimhoff, S.D.
A1 - Grein, F.
T1 - Study of the hyperfine coupling constants \(^{14}\)N and \(^1\)H) of the NH\(_2\) molecule in the X\(^2\)B\(_1\) ground state and the A\(^2\)A\(_1\) excited state
N2 - The hyperfine coupling constants (hfcc) A\(_{iso}\) and A\(_{ij}\) are calculated for the atoms of NH\(_2\) in its, two lowest-lying electronk states at various molecular geometries by means of the ab initio multireference configuration interaction .method. The vibronically averaged values of the hfccs for the K = 0 and 1 levels in \(^{14}\)N \(^1\)H\(_2\) in the energy range up to 20 000 cm\(^{-1}\) are computed. Polarization elfects which determine A\(_{iso}\) as well as a simple model to describe the dipolar hfccs are discussed. All resrilts are in excellent agreement with experimental data.
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58937
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
T1 - Ab initio calculations of the vibronically averaged values for the hyperfine coupling constants in NH\(_2\), NHD and ND\(_2\)
N2 - Vibronically averaged values for K =0 and K = 1 bending levels in the energy range between 0 and 25 000 cm\(^{-1}\) are computed for the \(^{14}\)N, H, and D atoms in NH\(_2\), NHD, and ND\(_2\) The pure ab initio electronic potentials, as well as those derived by fitting of experimentally observed band positions are employed. Effects of vibronic coupling and local perturbations of close-lying levels belanging to different electronic states are discussed.
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58941
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
T1 - Ab initio calculation of the vibronically averaged hyperfine coupling constants in the 1\(^2\)Π\(_u\) electronic state of CH\(_2 ^+\)
N2 - The results of pure ab initio calculations of the hyperfine coupling constants for the 1 \(^2 \pi _u\) electronic state for various isotopomers of CHi in the energy range between 0 and 20 000 cm\(^{-1}\) are presented. Effects of vibronic and spin-orbit coupling are discussed.
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58951
ER -
TY - JOUR
A1 - Stangl, R.
A1 - Jelinek-Fink, H.
A1 - Christl, Manfred
T1 - Darstellung phenylsubstituierter Derivate des Tricyclo[4.1.0.0\(^{2,7}\)]heptans und des 1,2,3,4-Tetrahydro-1,2,3-methenonaphthalins
N2 - No abstract available
KW - Organische Chemie
KW - Bicyclo[3.2.0.02
KW - 7]heptane derivatives
KW - Norcaranes
KW - 7
KW - 7-dibromo
KW - lH-Cyclopropa[a]naphthalenes
KW - 1
KW - 1-dibromo-1a
KW - 2
KW - 3
KW - 7b-tetrahydro-
KW - Carbene insertion
KW - Bicyclo[1.1.0]butane derivatives
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58610
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Stangl, R.
A1 - Jelinek-Fink, H.
T1 - Zur Kenntnis der thermischen Umlagerung des Bicyclo[1.1.0]butan-Systems. Eine kinetische Studie des Übergangs von Tricyclo[4.1.0.0\(^{2,7}\)]heptanen in Bicyclo[3.2.0]hept-6-ene
T1 - On the Thermal Rearrangement of the Bicyclo[1.1.0]butane System. A Kinetic Investigation of the Conversion of Tricyclo[4.1.0.0\(^{2,7}\)]heptanes into Bicyclo[3.2.0)hept-6-enes
N2 - No abstract available
KW - Organische Chemie
KW - 3-Methenonaphthalenes
KW - 4-tetrahydro-
KW - kinetics of thermolysis
KW - Benzocycloheptene derivatives
KW - Bicyclo[1.1.0]butanes
KW - rearrangement
KW - Tricyclo[4.1.0.02.7]heptanes
KW - kinetics of thermolysis
KW - Bicyclo[3.2.0]hept-6-ene derivatives
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58623
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Braun, Martin
A1 - Müller, Germar
T1 - 1,2,4-Cyclohexatriene, an Isobenzene, and Bicyclo[4.4.0)deca-1,3,5,7,8-pentaene, an Isonaphthalene: Generation and Trapping Reactions
N2 - No abstract available
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58639
ER -
TY - JOUR
A1 - Hegmann, J.
A1 - Ditterich, E.
A1 - Hüttner, G.
A1 - Christl, Manfred
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - δ-Chlor-δ-lactone aus γ-Oxoketenen
N2 - No abstract available
KW - Organische Chemie
KW - 1
KW - 3
KW - 4-0xadiazine-2-carboxylate
KW - methyl 6-oxo-5-phenyl-
KW - Diels-Alder reactions
KW - Ketenes
KW - y-oxo-
KW - δ-Lactones
KW - δ-chloro-
KW - β-Lactones
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58649
ER -
TY - JOUR
A1 - Bündgen, P.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - An MRD-CI study of low-lying electronic states in CaF
N2 - Dipole moments and various spectroscopic constants of some low-lying electronic states of the CaF molecule have been calculated using the multireference single· and double-excitation configuration-interaction (MRD-CI) method. The electronic structure of the highly ionic molecule in various excited states can be explained in tenns of different polarisations of the mainly Cacentered valence electron in the field of the F\(^-\) anion. Plots of natural orbitals occupied by the valence electron in the different states give a qualitative picture of the charge distribution and provide a visualisation of the different polarisations of the valence electron in the various states. Comparisons with the electrostatic polarisation model ofTörring, Ernstand Kändler (TEK model) are made. The unknown A' \(^2 \Delta\) state is predicted to lie about 21200 cm\(^{-1}\) above the ground state.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58880
ER -
TY - JOUR
A1 - Engels, Bernd
T1 - Estimation of the influence of the configurations neglected within truncated MR-CI wavefunctions on molecular properties
N2 - Reliable prediction of the isotropic hyperfine coupling constant, a\(_{iso}\), is still a difficult task for ab initio calculations. Strong dependence on the method used for its calculation is found. Within a truncated multi-referencc ansatz a\(_{iso}\) is strongly affected by the size ofthe reference space and the nurober of terms in the truncated Cl expansion. In the present paperdifferent effects of the neglected Cl space are discussed. Modified B\(_K\) and A\(_K\) methods are used to estimate the contributions ofthe neglected configurations. lt can be shown that a combination of both methods is able to recover about 90-9 S% of the total error in a\(_{iso}\)· Furthermore, it was found that to obtain about 90% of the B\(_K\) correction only about I 0-20% ofthe configurations within H0 have to be corrected.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58890
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio investigation of the vibronic structure of the C\(_2\)H spectrum Calculation of the hyperfine coupling constants for the three lowest lying electronic states
N2 - The hyperfine coupling constants (isotropic hfcc and four Cartesian components of the ani~ tropic tensor) are calculated for all three atoms of C\(_2\)H in its three lowest-lying electronic states at various molecu)ar geometries by means of the ab initio configuration interaction ( MRO.CI) method. The off-diagonal electronic matrix elements involving the two species ofthe A' symmetry are also computed. A diabatic transforrnation is perforrned Jeading to simple geometrical depen· dences of the hyperline coupling constants.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58901
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio investigation of the vibronic structure of the C\(_2\)H spectrum Computation of the vibronically-averaged values for the Hyperfine Coupling Constants
N2 - The vibronically averaged values for tbe hyperfine coupling constants in the X\(^2 \sum\)-A\(^2 \Pi\) system of the ethynyl radical are computed by means of tbe ab initio metbod calculations. The results point at tbe importance of taking into account the coupling of a1l tbree electronic states in question ( I\(^2\)A', 2\(^2\)A', and 1\(^2\)A") for a reliable explanation of the available experimental findings. The mean values of the hfcc's for K = 0 and 1 levels in \(^{13}\)C\(_2\)H and \(^{13}\)C\(_2\)D in the energy range up to 6000 cm\(^{-1}\) are predicted.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58915
ER -
TY - JOUR
A1 - Reuchlein, H.
A1 - Kraft, A.
A1 - Christl, Manfred
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Reaktionen von Bicyclo[2.1.1]hexenen mit 1,3,4-Oxadiazin-6-onen und dynamische Effekte einem in neungliedrigen, überbrückten, α,β-ungesättigten Enollacton
N2 - No abstract available
KW - Organische Chemie
KW - 1
KW - 3
KW - 4-0xadiazin-6-ones
KW - Diels-Alder reactions
KW - Enol Iactones
KW - Lactone conformations
KW - Line-shape analysis
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58577
ER -
TY - JOUR
A1 - Markgraf, J. H.
A1 - Cort, J. R.
A1 - Davis, H. A.
A1 - Lindeman, N. I.
A1 - Myers, C. R.
A1 - Kraft, A.
A1 - Christl, Manfred
T1 - Strained Heterocyclic Systems. 20. Basicities of Bicyclic Quinoxalines
N2 - No abstract available
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58584
ER -
TY - JOUR
A1 - Bentley, T. W.
A1 - Christl, Manfred
A1 - Norman, S. J.
T1 - Methanesulfonate/p-Nitrobenzoate and p-Toluenesulfonate/p-Nitrobenzoate Rate Ratios. Solvolyses of 1-Adamantyl and Benzhydryl Substrates
N2 - No abstract available
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58599
ER -
TY - JOUR
A1 - Jelinek-Fink, H.
A1 - Christl, Manfred
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Cycloallene, 7 : Ein Siebenringallen-Dimer: Darstellung aus einem 7,7-Dibromnorcaran-Derivat und Thermolyse
T1 - Cycloallenes, 7 : A Seven-Membered-Ring Allene Dimer: Preparation from a 7,7-Dibromonorcarane Derivative and Thermolysis
N2 - No abstract available
KW - Organische Chemie
KW - Bisbenzo[ 4
KW - 5]cyclohepta[ 1
KW - 2-α:2'
KW - 1' -c]naphthalene
KW - hexahydro-
KW - 7-Norcaranylidene carbenoid
KW - substituted
KW - Cycloallene dimerization
KW - Tetrakis(arylmethylene)ethane diradical
KW - 1
KW - 2-Bismethylenecyclobutanes
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58603
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
A1 - Skell, P.S.
T1 - Theoretical study of the potential energy surface governing the stereochemistry in ClC\(_2\)H\(_4\) reactions
N2 - Large-scale multireference configuration interaction calculations in a double·t·type AO basis including polarization functions are carried out for the potential surface of the ClC\(_2\)H\(_4\9 system. The charge distribution for various extreme points of the surface is discussed. The absolute minimum is found for an asymmetric ClC2H4 structure. The symmetrical bridged nuclear conformation is also found to be stable with respect to dissociation into Cl + C\(_2\)H\(_4\)• The activation energy for rotation about the C-C axis is calculated tobe around 18 kJ/mol, which is comparable tothat for the 1,2 migration {around 26 kJ/mol). The stereochemistry is governed by the fact that addition of CI to C\(_2\)H\(_4\) (or dissociation) is a two-step reaction proceeding through a symmetrica1 intermediate. The direct addition pathway possesses a small barrier of about 8 kJ jmol.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58851
ER -
TY - JOUR
A1 - Kim, E.
A1 - Christl, Manfred
A1 - Kochl, J. K.
T1 - Charge-Transfer Cycloaddition of Homobenzvalene with Tetracyanoethylene
N2 - The transient yellow color observed in the cycloaddition of homobenzvalene (HB) with tetracyanoethylene (TCNE) is associated with the charge-transfer complex [HB, TCNE). The deliberate photoexcitation of [HB,TCNE) affords a mixture of charge-transfer cycloadducts (1, 2, and 3) that differs from that obtained in thermal cycloaddition. The relationship of {HB t TCNE•) radical-ion pair (as the critical reactive intermediate in charge-transfer cycloaddition) to the activation process for thermal cycloaddition is discussed.
KW - Organische Chemie
KW - Electron transfer
KW - photochemical
KW - Radical-ion pair
KW - Photochemistry
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58537
ER -
TY - JOUR
A1 - Karna, S.P.
A1 - Grein, F.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio configuration-interaction studies of the ground state potential energy and hyperfine coupling constants of \(^{35}\)Cl\(_2^-\)
N2 - Potential energy and spectroscopic constants for the X\(^2 \sum^+ _\mu\) ground state of a;, were calculated by configuration-interaction (Cl) methods, using large basis sets with polarization and diffuse functions. From these CI wavefunctions, the isotropic (a\(_{iso}\)) and dipolar (A\(_{dip}\)) components of the hyperfine coupling constant were obtained. The effects of various s, p basis sets, polarization and diffuse functions, as well as the influence of reference configurations and configuration selection thresholds were investigated. The best values obtained are 35·31 G for a\(_{iso}\) and 29·440 for A\(_{dip}\)• tobe compared with experimental values of 37 ± 1 G and 32 ± 1 G, respectively. It is shown that the contributions to a1so of the K and L shells are opposite in sign, differing by about 4 G. Upon vibrational averaging, both a\(_{iso}\) and A\(_{dip}\) move towards smaller values as v increases. An adiabatic electron affinity of 2·46eV was obtained for CL\(_2\) , and a vertical electron detachment energy of 3·71 eV for Cl;.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58869
ER -
TY - JOUR
A1 - Funken, K.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
A1 - Grein, F.
T1 - Study of the hyperfine coupling constants of the moleculs NH2, NHD and ND2
N2 - In the present paper we c:alculate tbe magnetic hyperfine couplina constants (hfcc) ai.ID and A11 of the ground states of the isotopes NH2, NHD and ND2 using truncated MR..CI methods. Differences from other theoretical methocls and shortoominp of the truncated Cl approach in calculating tlj10 are studied. Polarization effects wbich detennirae ailo. as weU as a simple model to describe the dipolar hfcc's, are discussed. All results are in. excellent aareement with experimental data. lt is shown that ab initio methods are able to obtain reliable values for otf-diaaonal values of A41 which are difficult to measure experimentaDy.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58875
ER -
TY - JOUR
A1 - Lang, R.
A1 - Herzog, C.
A1 - Stangl, R.
A1 - Brunn, E.
A1 - Braun, M.
A1 - Christl, Manfred
A1 - Peters, K.
A1 - Peters, E.-M.
A1 - Schnering, H. G. von
T1 - Reaktionen von Homobenzvalenen mit 4-Phenyl-3H-1,2,4-triazol-3,5(4H)-dion, Tetracyanethylen, Chlorsulfonylisocyanat und Schwefeldioxid. Einige konzertierte 1,4-Additionen an eine Vinylcyclopropan-Einheit
T1 - Reactions of Homobenzvalenes wlth 4-Phenyl-3H-1,2,4-trlazole-3,5(4H)-dione, Tetracyanoethylene, Chlorosulfonyl Isocyanate, and Sulfur Dioxide. Several Concerted 1,4-Additions to a Vinylcyclopropane Subunit
N2 - No abstract available
KW - Organische Chemie
KW - 6-Thiatricyclo[3.2.1.o 2.7 ]oct-3-ene 6
KW - 6-dioxide
KW - Homo Diels-Alder reactions
KW - Cyclopropanetetracarbonitrile derivatives
KW - Barbaralane derivatives
KW - Urazoles
KW - polycyclic
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58527
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Reuchlein, H.
T1 - Synthesis and NMR Spectra of 2,3-Dihydro-1,3-methanoindene Derivatives and 1,2,3,5-Tetrahydro-1,3-methanopentalene
N2 - No abstract available
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58557
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Lanzendörfer, U.
A1 - Grötsch, M. M.
A1 - Ditterich, E.
A1 - Hegmann, J.
T1 - Cycloadditionen von 1,3,4-0xadiazin-6-onen (4,5-Diaza-alpha-pyronen), 9 - 6-Oxo-5-phenyl-1,3,4-oxadiazin-2-carbonsäure-methylester - Synthese und Reaktionen mit Norbornen, Norbornadien, Cyclopropenen, Cyclobuten und Benzvalen
N2 - No abstract available
KW - Organische Chemie
KW - 1
KW - 3
KW - 4-0xadiazin-6-ones
KW - Diels-Alder reactions
KW - y-Oxoketenes
KW - ß-Lactones
KW - bicyclic
KW - Enol Iactones
KW - alpha
KW - ß-unsaturated
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58569
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Reuchlein, H.
T1 - Synthesen und NMR-Spektren von 2,3-Dihydro-1,3-methanoindenderivaten und 1,2,3,5-Tetrahydro-1,3-methanopentalen
N2 - No abstract available
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58549
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Theoretical study of FC\(_2\)H\(_4\)
N2 - Large-scale multireference configuration interaction (MRD-CI) calculations in a quite flexible AO basis are employed to study the energy hypersurface for the reaction intermediate FC\(_2\)H\(_4\) • The reaction F + C\(_2\)H\(_4\) -> FC\(_2\)H\(_4\) as weil as the 1,2 migration of the fluorine atom in FC\(_2\)H\(_4\) is investigated. In addition the rotation around the CC bond in the optimum conformation is studied. The absolute minimum in the potential energy is found for the asymmetric structure but the symmetric structure is also found to be stable with respect to the dissociation, so that a shuttling of the fluorine atom is in principle possible but highly unlikely because ( l) the activation energy is high ( II 5-130 kJ fmol) and the saddle point lies only 4(}-50 kJ jmol below the dissociation Iimit of F + C\(_2\)H\(_4\) and (2) the competitive motion, i.e., rotation around the CC axis, is nearly free (I 1-17 kJ/mol).
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58824
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - The hyperfine coupling constants of the X\(^3\)Σ\(^-\) state of NH : Influence of polarization functions and configuration space on the description of spin polarization
N2 - The hyperfine coupling constants for the \(^3\)Σ\(-\) ground state of the NH molecule are determined by configuration interaction calculations whereby the infl.uence of polarization functions as weil as of the configuration space on the spin polarization mechanism is analysed. The dipolar part Au(N) and Au(H) can be obtained very reliably without much computational effort (A .. (N) == -45·3 MHz and A"(H) = -62·3 MHz). The value for the isotropic contribution a1.., in the best AO basis and MRD-CI treatment is - 64·5 MHz for H and 16·6 MHz for nitrogen compared to the corresponding experimental quantities of -66 MHz and 19 MHz respectively. Their determination depends on a subtle balance of the lu, 2u and 3u shell correlation description, whereby the dominant contribution to a1..,(H) results from the 2u shell. It is shown that the often good agreement of a110 values with experiment in a small basis singledouble configuration interaction treatment results from a cancellation of two errors.
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58832
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Study of orbital transformations in configurational interaction calculation of hyperfine coupling in nitrogen and CH molecule
N2 - Multi-reference configuration interaction calculations employing various orbital transformations are undertaken to obtain the isotropic hyperfine coupling constant a\(_{iso\) in nitrogen and a\(_{iso\) (H) in the CH molecule. The natural orbital (NO) basis is found to be more effective than the simple RHF-MO basis; the most obvious is a basis of spin natural orbitals (SNO). It is found that a\(_{iso\) is approached from opposite sides in the NO and 2s shell SNO basis if the CI expansion is increased. Both results are within a few percent of the full CI Iimit for the nitrogen atorn (in the given AO basis) and the experimental value for Hin the CH radical. Various features ofthe SNO are discussed.
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58847
ER -
TY - JOUR
A1 - Karna, S.
A1 - Grein, F.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - The hyperfine coupling constants of \(^{19}\)F\(_2\)
N2 - The isotropic (a\(_{iso}\)) and dipolar (A\(_{dip}\)) hyperfine coupling constants of 19F2 were obtained from MRD-CI wave functions using a variety of basis sets. In series I, increasing numbers of d functions were added to a 5s4p contracted Huzinaga!Dunning basis. In series II, the 5s3p basis set was uncontracted in several steps until 9s5p was reached, to which were added from one to three d-polarization functions. Cl parameters (selectioo threshoids and the number of reference coofiguratioos) were also varied. A study of the R dependence of aiso and Adip was perfonned. The best values obtained at R\(_e\) are 260 G for a\(_{iso}\) and 308 G for A\(_{dip}\)• compared with experimental values of about 280 G for a;10 and 320 G for A\(_{dip}\)·
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58817
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Brunn, E.
A1 - Roth, W. R.
A1 - Lennartz, H.-W.
T1 - 7-Methyl- and 7-Phenylcyclohepta-1,3,5-trienes from Benzvalene Via 3,3a,4,5,6,6a-Hexahydro-4,5,6-methenocyclopentapyrazoles and Tetracyclo[4.1.0.0\(^{2,4}\).0\(^{3,5}\)]heptanes
N2 - No abstract available
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58471
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Brunn, E.
A1 - Kraft, A.
A1 - Irngartinger, H.
A1 - Huber-Patz, U.
T1 - Nichtbindende Wechselwirkungen in zwei 7-Spirotetracyclo[4.1.0.0\(^{2,4}\).0\(^{3,5}\)]heptanen
T1 - Nonbonded Interactions in two 7-Spirotetracyclo[4.1.0.0\(^{2,4}\).0\(^{3,5}\)]beptanes
N2 - Die Reaktion von Tetrachlordiazocyclopentadien mit Be.nzvalen (2) ergab das Fulven-Derivat 3. Dagegen führten die Umsetzungen von Diazoßuoren und 5-Diazo-10,1 1-dihydro-SH-dibenzo[ a.d]cyclohepten mit 2 zu den erwarteten Spiro-1-pyrazolinen 4 bzw. 5. Die photolytische Abspaltung von Stickstoff aus 4 und 5 lieferte die Spirotetracycloheptane 6 bzw. 7. Die Röntgenstrukturanalyse von 6 beweist einen engen Kontakt zwischen je eineßl Wasserstoffatom der Tetracycloheptan- und der Fluoren-Einheit. Dieser kurze Abstand (2.15 A) ruft Winkelaufweitungen hervor und wird auch als Grund für starke Entschirmungen der betreffenden Protonen und eine formal über sieben Bindungen reichende 0.6-Hz-Kopplung zwischen ihnen angesehen. 7 ist das erste chiralc Tetracyclohcptan. Ursache dafür ist eine nichtebene Konformation des Siebenrings, der bei Raumtemperatur nicht invertiert. Auf der Basis von NOE-Messungen gelang die Zuordnung der tH-NMR-Signale von 6 und 7.
N2 - The reaction or tctrachlorodiazocyclopentadiene with benzvalene (2) gavc, the fulvene derivative 3. In contrast, treatment of diazoßuorene and 5-diazo-1 0,1 1-dihydro·SH -dibenzo[ a,d]cycloheptene with l:afl'orded the expected spiro-1-pyrazolines 4 and 5, respectively. Photolytic extrusion of nitrogen from 4 and S led to the corresponding spirotetracyclobeptanes 6 and 7. The X-ray structure analysis of 6 revealed a close contact between one hydrogen atom cach of the tetracycloheptane and the ßuorene subunits. This short distance (2.15 A) causes an increase in bond angles and is believed to produce strong deshielding of the respective protons and a 0.6-Hz coupling between them, which is formally a long-range coupling across seven bonds. Compound 7 is the first chirat tetracycloheptane. This is due to a nonplanar confonnation of the seven-membered ring, which does not invert at room temperature. On tbe basis of NOE measurements the 1H-NMR signals of 6 and 7 are assigned.
KW - Organische Chemie
KW - 5H-Dibenzo[a
KW - d]cycloheptene
KW - 10
KW - 11-dihydro- / 1-Pyrazoline
KW - Nonbonded Interactions
KW - Spirotetracyclo[4.1.0.02
KW - 4.03
KW - 5]beptanes
KW - Long-range coupling constants
KW - mtrogen extruston
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58489
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Braun, Max
T1 - Photocycloadditionen des Benzvalens
N2 - No abstract available
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58492
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Braun, Max
T1 - Photocycloadditions of Benzvalene
N2 - No abstract available
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58506
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Braun, Martin
T1 - Freisetzung und Abfangreaktionen von 1-Oxa-2,3-cyclohexadien
T1 - Generation and Interception of 1-0xa-2,3-cyclohexadiene
N2 - Umsetzung von 6,6-Dichlor-2-oxabicyclo[3.1.0)hexan (4a) in Styrol mit n-Butyllithium lieferte neben Polystyrol und t-Chlor-1- pbenylhexan (6) in geringer Ausbeute die Tet~hydrocyclobutapyrane 5, die Abfangprodukte des aus 4a generierten t-Oxa-2,3- cyclobexadiens (3). Das unbeständige 6,6-Dibrom-2-oxabicyclo( J.l.O]hexan (4b) wurde bei -60°C erzeugt un~ bei -30°C mit Methyllithium in Gegenwart von Styrol umgesetzt, woraus die Produkte 5 mit 24% Ausbeute hervorgingen. Als bei 20°C beständige Quelle für 3 erwies sich exo-6-Brom-e~o-6-fluor-2-oxabicyclo[ J.t.O]bexan (9), das aus 2,3-Dihydrofuran und Bromßuorcarben mit 25% Ausbeute bereitet wurde. Behandlung von 9 in Styrol,