@article{KoetzGuentherKosmellaetal.2004, author = {Koetz, Joachim and G{\"u}nther, Claudia and Kosmella, Sabine and Kleinpeter, Erich and Wolf, Gunter}, title = {Polyelectrolyte induced structural changes in the isotropic phase of the system sulfobetaine/pentanol/toluene/ water}, year = {2004}, language = {en} } @article{VirtaKochRoslundetal.2005, author = {Virta, P. and Koch, Andreas and Roslund, M. U. and Mattjus, P. and Kleinpeter, Erich and Kronberg, L. and Sjoholm, R. and Klika, Karel D.}, title = {Synthesis, characterisation and theoretical calculations of 2,6-diaminopurine etheno derivatives}, issn = {1477-0520}, year = {2005}, abstract = {Four derivatives of 2,6-diaminopurine (1) were synthesised and characterised. When 1 was reacted with chloroacetaldehyde, 5-aminoimidazo[2,1- i] purine (2), 9-aminoimidazo[2,1-b]purine (3), 9-aminoimidazo[1,2- a]purine (4) and diimidazo[2,1-b: 2', 1'-i]purine (5) were formed. The purified products (3 - 5) were fully characterised by MS, complete NMR assignments as well as fluorescence and UV spectroscopy. The purified, isolated yields of these products ( 3 - 5) varied from 2.5 to 30\%. The relative stability of different tautomers was investigated by theoretical calculations. Fluorescence characteristics are also discussed and compared to the starting material 1 and a reference molecule 2-aminopurine}, language = {en} } @article{WolfKleinpeter2005, author = {Wolf, G. and Kleinpeter, Erich}, title = {Pulsed field gradient NMR study of anomalous diffusion in a lecithin-based microemulsion}, issn = {0743-7463}, year = {2005}, abstract = {Self-diffusion measurements in microemulsion systems composed of a naturally occurring soybean lecithin mixture, an aqueous phase, either water or a 1\% aqueous PDADMAC solution, and isooctane were accomplished by pulsed field gradient (PFG) (HNMR)-H-1 spectroscopy at oil dilution lines of low and intermediate water/lecithin ratios. The concentration-dependent diffusion data reveal water-in-oil (W/O) reverse micellar aggregates with dimensions on the nanometer scale being slightly smaller at low water content. With increasing micellar volume fractions, both hydrodynamic as well as direct interactions between particles significantly slow aggregate diffusion. The surfactant mean square displacements (msd's) in dilute and concentrated polymer-free systems studied as a function of diffusion time (20-1000 ms) are characterized by a crossover from Gaussian diffusion, due to slow aggregate motion, to anomalously enhanced diffusion, due to fast surface-bulk surfactant exchange at intermediate times revealing weak, barrier-controlled adsorption behavior. Upon addition of the polycation PDADMAC, the diffusion characteristics change to exclusively superdiffusive behavior with surfactant msd scaling with time as t(3/2) over the entire time range studied. This is caused by surfactant molecules performing Levy walks along the surface of reverse micelles mediated by the dilute bulk. The bulk-mediated surface diffusion is a consequence of the diffusion-controlled micelle-bulk exchange dynamics induced by interactions of PDADMAC with surfactant headgroups}, language = {en} } @article{ThomasKleinpeter2005, author = {Thomas, Steffen and Kleinpeter, Erich}, title = {A novel empirical approach for the structure elucidation of disilanes by empirical estimation of their Si-29 chemical shifts}, issn = {0022-2860}, year = {2005}, abstract = {In C-13 NMR spectroscopy, there are many empirical methods for fast and exact computation of C-13 chemical shifts; comparable procedures for Si-29 NMR chemical shifts are not existing or are older than 20 years. On basis of the largest database of Si-29 chemical shifts available, along this paper a relatively simple procedure for the similarly exact calculation of the Si-29 chemical shifts of disilanes (average margin of error ca. 3.7 ppm) is given. (c) 2005 Elsevier B.V. All rights reserved}, language = {en} } @article{TaddeiKleinpeter2005, author = {Taddei, F. and Kleinpeter, Erich}, title = {The anomeric effect in substituted cyclohexanes : II. The role of hyperconjugative interactions and steric effect in 1,4-disubstituted cyclohexanes}, issn = {0166-1280}, year = {2005}, abstract = {The conformational equilibria of the cis/trans isomers of some 1,4-di-substituted cyclohexanes (X = OH, OMe, Me, OCOCH3, OCOC(CH3)(3), OCOCCl3, OCOCF3) were calculated at several levels of theory; the best correlation between calculated and experimentally available Delta G(0)s refers to the MP2/6-311 +G*//MP2/6-311G* results. In addition, the hyperconjugative effect of the substituents was studied with the NBO options included in the GAUSSIAN-98 package; a number of interactions between filled NBOs and antibonding orbitals could be considered as most representative for delocalization along the molecules studied. The effect of the substituents on the molecular geometry of the substituted cyclohexanesas well as the partitioning of both hyperconjugative and steric substituent effects on the present conformational equilibria is critically evaluated. Our model [E. Kleinpeter, F. Taddei, J. Mol. Struct. (THEOCHEM) 683 (2004) 29] for interpreting the relative stability of conformers of substituted cyclohexanes could be further verified and its reliability assessed. (c) 2005 Elsevier B.V. All rights reserved}, language = {en} } @article{SeidlCarneiroTostesetal.2005, author = {Seidl, Peter Rudolf and Carneiro, J. W. D. and Tostes, J. G. R. and Koch, Andreas and Kleinpeter, Erich}, title = {Interpretation of conformational effects on 2-endo-norborneol by natural chemical shielding analysis}, issn = {1089-5639}, year = {2005}, abstract = {This paper represents an extension of our work on the H-1 and C-13 NMR chemical shifts of norbornane and 2-endo- norborneol. NCS-NBO analysis was employed to probe contributions of bond orbitals and orbitals of lone pairs to nuclear shielding in conformers of the alcohol generated by rotation of the C-O bond. Variations in H-1 and C-13 chemical shifts with the dihedral angle are discussed in terms of Lewis and non-Lewis partitioning and their respective importance is evaluated. In addition to hyperconjugation of the lone pair in a p orbital of oxygen that was previously reported, a sizable participation of the lone pair which is in an sp orbital is also observed and their combined effect dominates the carbon chemical shifts of the C-1-C-2-OH and C-3-C-2-OH fragments. Both lone pairs on oxygen also contribute to localized, though-space effects on nuclei in the vicinity, these effects answering for the largest deviations in hydrogen chemical shifts on rotation around the C-O bond. On the other hand, for conformers in which nonbonded repulsions lead to distortions in the molecular framework, variations in chemical shifts may be attributed to angular effects}, language = {en} } @article{RyppaSengeHatscheretal.2005, author = {Ryppa, C. and Senge, Mathias O. and Hatscher, S. S. and Kleinpeter, Erich and Wacker, Philipp and Schilde, Uwe and Wiehe, A.}, title = {Synthesis of mono- and disubstituted porphyrins : A- and 5,10-A(2)-type systems}, issn = {0947-6539}, year = {2005}, abstract = {General syntheses have been developed for meso-substituted porphyrins with one or two substituents in the 5,10- positions and no beta substituents. 5-Substituted porphyrins with only one meso substituent are easily prepared by an acid-catalyzed condensation of dipyrromethane, pyrrole-2-carbaldehyde. and an appropriate aldehyde using a "[2+1+1]" approach. Similarly, 5,10-disubstituted porphyrins are accessible by simple condensation of unsubstituted tripyrrane with pyrrole and various aldehydes using a "[3+1]" approach. The yields for these reactions are low to moderate and additional formation of either di- or mono-substituted porphyrins due to scrambling of the intermediates is observed. However, the reactions can be performed quite easily and the desired target compounds are easily removed due to large differences in solubility. A complementary and more selective synthesis involves the use of organolithium reagents for SNAr reactions. Reaction of in situ generated porphyrin (porphine) with 1.1-8 equivalents of RLi gave the monosubstituted porphyrins, while reaction with 3-6 equivalents of RLi gave the 5,10-disubstituted porphyrins in yields ranging from 43 to 90\%. These hitherto almost inaccessible compounds complete the series of different homologues of A-, 5,15-A(2)-, 5,10-A(2)-, A(3)-, and A(4)-type porphyrin's and allow an investigation of the gradual influence of type, number, and regiochemical arrangement of substituents on the properties of meso-substituted porphyrins. They also present important starting materials for the synthesis of ABCD porphyrins and are potential synthons for supramolecular materials requiring specific substituent orientations}, language = {en} } @article{NeuvonenNeuvonenKochetal.2005, author = {Neuvonen, Helmi and Neuvonen, Kari and Koch, Andreas and Kleinpeter, Erich}, title = {Ab initio study of the substituent effects on the relative stability of the E and Z conformers of phenyl esters : Stereoelectronic effects on the reactivity of the carbonyl group}, issn = {1089-5639}, year = {2005}, abstract = {Equilibria between the Z (tau(1) = 0 degrees) and E (tau(1) = 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, Delta E(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mot(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between Delta E of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (n(O) -> pi*(C=O)) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The n(O) -> pi*(C=O) electron donation has a minimum value with tau(1) = 90 degrees and a maximum value with tau(1) = 90 degrees (the Z conformer), the value with tau(1) = 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*(C=O) antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*(C=O) occupancies of the ester series 4 and}, language = {en} } @article{KleinpeterSchulenburgZugetal.2005, author = {Kleinpeter, Erich and Schulenburg, Anja and Zug, Ines and Hartmann, Horst}, title = {The interplay of thio(seleno)amide/vinylogous thio(seleno)amide "Resonance" and the anisotropic effect of thiocarbonyl and selenocarbonyl functional groups}, issn = {0022-3263}, year = {2005}, abstract = {[GRAPHICS] Amino-substituted thio(seleno)acrylamides 1-4 were synthesized and their H-1 and C-13 NMR spectra assigned. Both the NMR data and the results of theoretical calculations at the ab initio level of theory were employed to elucidate the adopted structures of the compounds in terms of E/Z isomerism and s-cis/s-trans configuration. In the case of the asymmetrically N(Me)Ph-substituted compounds, ab initio GIAO-calculated ring current effects of the N-phenyl group were applied to successfully determine the preferred conformer bias. The restricted rotations about the two C-N partial double bonds were studied by DNMR and the barriers to rotation (Delta G(c)(double dagger)) determined at the coalescence temperatures, and these were discussed with respect to the structural differences between the compounds. The barriers to rotation were also calculated at the ab initio level of theory where the best results (R-2 = 0.8746) were obtained only with inclusion of the solvent at the SCIPCMHF/6-31G* level of theory. The calculations also provided means of assessing structural influences which were not available due to inaccessible rotation barriers. By means of natural bond orbital (NBO) analysis of 1-4, the occupation numbers of nitrogen lone pairs and bonding/antibonding pi/pi* orbitals were shown to quantitatively describe thio(seleno)amide/vinylogous thio(seleno)amide "resonance". Finally, the thio(seleno)carbonyl anisotropic effect was quantitatively calculated by the GIRO method and visualized by isochemical shielding surfaces (ICSS). Only marginal differences between the two anisotropic effects were calculated and are therefore of questionable utility for previous and future applications with respect to stereochemical assignments}, language = {en} } @article{KleinpeterSchulenburg2005, author = {Kleinpeter, Erich and Schulenburg, A.}, title = {Quantification of the push-pull effect in substituted alkenes}, issn = {0040-4039}, year = {2005}, abstract = {The quotient of the occupation numbers of pi bonding and pi* antibonding orbitals of the central C=C partial double bond, pi*(C=C)/pi(C=C), proved to be a useful parameter to quantify the push-pull effect completely for the first time in substituted alkenes by examination of a comprehensive set of compounds. (c) 2005 Elsevier Ltd. All rights reserved}, language = {en} } @article{KleinpeterKochPihlaja2005, author = {Kleinpeter, Erich and Koch, Andreas and Pihlaja, Kalevi}, title = {Application of (1)J(C,H) coupling constants in conformational analysis}, issn = {0040-4020}, year = {2005}, abstract = {Conformational equilibria for a number of methyl substituted 1,3-dioxanes 1, 1,3-oxathianes 2 and 1,3-dithianes 3 were calculated at the HF and DFT levels of theory. In addition to the chair conformers also the energetically adjacent twist conformers were considered and the positions of the corresponding conformational equilibria estimated. On the basis of the global energy minima of conformers, participating in the conformational equilibria, the 1J(C,Hax,equ) coupling constants were calculated using the GIAO method and compared with the experimental values obtained from C-13, H- 1 coupled C-13 NMR spectra. The Perlin effect, the influence of the solvent and the suitability of this NMR parameter for assigning the conformational equilibria present are critically discussed. (c) 2005 Elsevier Ltd. All rights reserved}, language = {en} } @article{KlinkaImrichDaniheletal.2005, author = {Klinka, Karel D. and Imrich, Jan and Danihel, I. and Bohm, Stanislav and Kristian, Pavol and Harnul'akova, S. and Pihlaja, Kalevi and Koch, Andreas and Kleinpeter, Erich}, title = {Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl)iminothiocarbonate}, issn = {0749-1581}, year = {2005}, abstract = {The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S- allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the rNOE. Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case- by-case basis. Copyright (c) 2005 John Wiley \& Sons, Ltd}, language = {en} } @article{HeydenreichKochSarodnicketal.2005, author = {Heydenreich, Matthias and Koch, Andreas and Sarodnick, Gerhard and Kleinpeter, Erich}, title = {Quinoxalines XIV : Synthesis, H-1, C-13, N-15 NMR spectroscopic, and quantum chemical study of 1H-pyrazolo[3,4- b]quinoxalines (flavazoles)}, issn = {0040-4020}, year = {2005}, abstract = {The synthesis of a series of 1H-pyrazolo[3,4-b]quinoxalines (flavazoles) by acylation, alkylation, halogenation, and aminomethylation of the parent compound is reported and their structure is investigated by H-1, C-13 and N-15 NMR spectroscopy. The restricted rotation about the partial C, N double bond of the N-acyl derivatives 7-10 is studied by dynamic NMR spectroscopy and the barriers to rotation are determined. In order to assign unequivocally the 15 N chemical shifts of N-4 and N-9, in case of 3-substituted flavazoles, exemplary the H-1, C-13, and N-15 NMR chemical shifts of 34, 35, and 39 are also theoretically calculated by quantum chemical methods [ab initio at different levels of theory (HF/6-3G* and B3LYP/6-31G*)]. (C) 2005 Elsevier Ltd. All rights reserved}, language = {en} } @article{MarkovicBaranacStojanovicSteeletal.2005, author = {Markovic, Rade and Baranac-Stojanovic, Marija and Steel, Peter J. and Kleinpeter, Erich}, title = {Stereocontrolled synthesis of new tetrahydrofuro[2,3-d]thiazole derivatives via activated vinylogous iminium ions}, issn = {0385-5414}, year = {2005}, abstract = {Heterocyclization of (Z)-5-(2-hydroxyethyl)-3-methyl-4-oxothiazolidines, bearing electron-withdrawing groups conjugated to an exocyclic double bond at C(2)-position, afforded under reductive conditions, cis-tetrahydroftiro[2,3- d]thiazole derivatives. The reactions of these functionalized push-pull beta-enamines occur in a stereocontrolled fashion via activated vinylogous N-methyliminium ions, which are trapped by an internal hydroxyethyl group}, language = {en} } @article{NeuvonenFulopNeuvonenetal.2005, author = {Neuvonen, Kari and Fulop, Ferenc and Neuvonen, Helmi and Koch, Andreas and Kleinpeter, Erich and Pihlaja, Kalevi}, title = {Propagation of polar substituent effects in 1-(substituted phenyl)-6,7-dimethoxy-3,4-dihydro- and -1,2,3,4- tetrahydroisoquinolines as explained by resonance polarization concept}, year = {2005}, abstract = {Propagation of inductive and resonance effects of phenyl substituents within 1-(substituted phenyl)-6,7- dimethoxy-3,4-dihydro- and -1,2,3,4-tetrahydroisoquinolines were studied with the aid of C-13 and N-15 NMR chemical shifts and ab initio calculations. The substituent-induced changes in the chemical shift (SCS) were correlated with a dual substituent parameter equation. The contributions of conjugative (rho(R)) and nonconjugative effects (rho(F)) were analyzed, and mapping of the substituent-induced changes is given over the entire isoquinoline moiety for both series. The experimental results can be rationalized with the aid of the resonance polarization concept. This means the consideration of the substituent-sensitive balance of different resonance structures, i.e., electron delocalization, and the effect of the aromatic ring substituents on their relative contributions. With tetrahydroisoquinolines, the delocalization of the nitrogen lone pair (stereoelectronic effect) particularly contributes. Correlation analysis of the Mulliken atomic charges for the dihydroisoquinoline derivatives was also performed. The results support the concept of the substituent-sensitive polarization of the isoquinoline moiety even if the polarization pattern achieved via the NMR approach is not quite the same as that predicted by the computational charges. Previously the concepts of localized pi- polarization and extended polarization have been used to explain polar substituent effects within aromatic side-chain derivatives. We consider that the resonance polarization model effectively contributes to the understanding of the polar substituent effects}, language = {en} } @article{KleinpeterSeidl2005, author = {Kleinpeter, Erich and Seidl, Peter Rudolf}, title = {The gamma- and the delta-effects in C-13 NMR spectroscopy in terms of nuclear chemical shielding (NCS) analysis}, issn = {0894-3230}, year = {2005}, language = {en} } @article{KlinkaBalentovaBernatetal.2006, author = {Klinka, Karel D. and Balentova, Eva and Bern{\´a}t, Juraj and Imrich, J{\´a}n and Vavrusov{\´a}, Martina and Pihlaja, Kalevi and Koch, Andreas and Kleinpeter, Erich and Kelling, Alexandra and Schilde, Uwe}, title = {Structural revision of products resulting from the reaction of methylhydrazine with acridin-9-yl isothiocyanate due to unexpected acridinyl migration And further reactions}, issn = {1551-7004}, year = {2006}, abstract = {The reaction of methyl acridin-9-ylthiosemicarbazide under basic conditions with methyl bromoacetate resulted in a 1,3-thiazolin-4-one structure as provided by X-ray crystallography. The structure forced a re-evaluation of the reactant methyl acridin-9-ylthiosemicarbazide, originally thought to be 2-methyl 4-acridin-9-ylthiosemicarbazide based on synthetic expectations, but which when examined by X-ray crystallography was found to be in fact the isomeric 2- methyl 1-acridin-9-ylthiosemicarbazide resulting from rearrangement via a spiro form which it is in equilibrium with in solution. The product resulting from reaction with methyl iodide was also studied and the previously reported semicarbazide produced by reaction with MNO was re-examined. In both cases, the 1,2 isomer rather than the 2,4 isomer was found to be present based on the sign of the 3JCH3,N11 coupling. Full characterization of the compounds was rendered by 1H, 13C, and 15N solution-state NMR, and in the solid state, by both 13C and 15N NMR.}, language = {en} } @article{Kleinpeter2006, author = {Kleinpeter, Erich}, title = {Push-pull alkenes : structure and pi-electron distribution}, doi = {10.2298/Jsc0601001k}, year = {2006}, abstract = {Push-pull alkenes are substituted alkenes with one or two electron-donating substituents on one end of C=C double bond and with one or two electron-accepting substituents at the other end. Allowance for pi-electron delocalization leads to the central C=C double bond becoming ever more polarized and with rising push-pull character, the pi-bond order of this double bond is reduced and, conversely, the corresponding pi-bond orders of the C-Don and C- Ace bonds are accordingly increased. This push-pull effect is of decisive influence on both the dynamic behavior and the chemical reactivity of this class of compounds and thus it is Of Considerable interest to both determine and to quantify the inherent push-pull effect. previously, the barriers to rotation about the C=C, C-Don and/or C-Acc partial double bonds (Delta G(not equal), as determined by dynamic NMR spectroscopy) or the C-13 chemical shift difference of the polarized C=C partial double bond (Delta delta(C=C)) were employed for this purpose, However, these parameters can have serious limitations, viz. the barriers can be immeasurable on the NMR timescale (either by being too high or too low-, heavily-biased conformers are present, etc.) or Delta delta(C=C) behaves in a non-additive manner with respect to the combination of the four substituents. Hence, a general parameter to quantify the push-pull effect is not yet available. Ab initio MO calculations on a collection of compounds, together with NBO analysis, provided valuable information on the structure, bond energies, electron occupancies and bonding/antibonding interactions. In addition to Delta G(C=C)(not equal) (either experimentally determined or theoretically calculated) and Delta delta(C=C), the bond length of the C=C partial double bond was also examined and it proved to be a reliable parameter to quantify the push-pull effect. Equally so, the quotient of the occupation numbers of the antibonding and bonding pi orbitals of the central C=C partial double bond ( pi*(C=C)/pi(C=C) ) could also be employed for this purpose}, language = {en} } @article{Kleinpeter2008, author = {Kleinpeter, Erich}, title = {Quantification of the (Anti)Aromaticity of Fulvalenes Subjected to -Electron Cross-Delocalization}, doi = {10.1021/Jo701520j}, year = {2008}, abstract = {Fulvalenes 3-12 were theoretically studied at the ab initio level of theory. For the global minima structures, the occupation of the bonding (pi)C=C orbital of the interring C=C double bond obtained by NBO analysis quantitatively proves pi-electron cross-delocalization resulting in, at least partially, 2- or 6pi-electron aromaticity and 8pi- electron antiaromaticity for appropriate moieties. The cross-conjugation was quantified by the corresponding occupation numbers and lengths of the interring C=C double bonds, while the aromaticity or antiaromaticity due to cross- delocalization of the pi-electrons was visualized and quantified by through-space NMR shielding surfaces.}, language = {en} } @article{ShainyanUshakovMeshcheryakovetal.2007, author = {Shainyan, Bagrat A. and Ushakov, Igor A. and Meshcheryakov, Vladimir I. and Schilde, Uwe and Koch, Andreas and Kleinpeter, Erich}, title = {The stereodynamics of 3,5-bis(trifluoromethylsulfonyl)-1,3,5-oxadiazinane and 1,3,5- tris(trifluoromethylsulfonyl)-1,3,5-triazinane- an experimental and theoretical study}, doi = {10.1016/j.tet.2007.09.041}, year = {2007}, abstract = {Multinuclear dynamic NMR spectroscopy of 3,5-bis(trifluoromethylsulfonyl)-1,3,5-oxadiazinane (3) revealed the existence of two conformers with differently oriented CF3 groups with respect to the ring, and two dynamic processes: ring inversion and restricted rotation about the N-S bond. Two transition states connecting the two conformers and corresponding to clockwise and counterclockwise rotations about the N-S bond were found; the calculated activation barriers of about 12 kcal/mol are in excellent agreement with those measured experimentally for the related molecule 1,3,5-tris(trifluoromethylsulfonyl)-1,3,5-triazinane (1). X-ray analysis proved the existence of the symmetric isomer of 3, which is the minor isomer in solutions but the only one in the crystal due to packing effects. The normal Perlin effect (JCHax < JCHeq)observed for 2(6)-CH2 in 3, whereas the reversed Perlin effect was found for the 4-CH2 group in 3 as well as for all CH2 groups in 1 both experimentally and theoretically. The latter effect in compounds 1, 3, and 1- (methylsulfonyl)-3,5-bis(trifluoromethylsulfonyl)-1,3,5-triazinane (2) can be considered as a genuine reverse Perlin effect since larger values of 1JCH are observed for longer C-H bonds.}, language = {en} } @article{KleinpeterKochMikhovaetal.2008, author = {Kleinpeter, Erich and Koch, Andreas and Mikhova, Bozhana and Stamboliyska, Bistra A. and Kolev, Tsonko M.}, title = {Quantification of the push-pull character of the isophorone chromophore as a measure of molecular hyperpolarizability for NLO applications}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2007.12.107}, year = {2008}, abstract = {The push-pull character of a series of para-phenyl substituted isophorone chromophores has been quantified by the 13C chemical shift difference of the three conjugated partial C=C double bonds and the quotient of the occupations of both the bonding and anti-bonding orbitals of these C=C double bonds as well. The correlations of the two push-pull quantifying parameters, and to the corresponding bond lengths, strongly recommend ;*c=c/ ;c=c as the general parameter to estimate charge alternation and as a very useful indication of the molecular hyperpolarizabilities for NLO application of the compounds studied.}, language = {en} } @article{NeuvonenFulopNeuvonenetal.2008, author = {Neuvonen, Helmi and Fulop, Ferenc and Neuvonen, Kari and Koch, Andreas and Kleinpeter, Erich}, title = {Electronic effects of heterocyclic ring systems as evaluated with the aid of 13C and 15N NMR chemical shifts and NBO analysis}, doi = {10.1002/Poc.1271}, year = {2008}, abstract = {The electronic effects of the 5- and 6-membered heterocyclic rings on the C=N-N unit of five different hydrazone derivatives of pyridine-2-, -3- and -4-carbaldehydes, pyrrole-2-carbaldehyde, furan-2- and -3-carbaldehydes and thiophene-2- and -3-carbaldehydes have been studied with the aid of 13C and 15N NMR measurements together with the natural bond orbital (NBO) analysis. As model compounds are used the corresponding substituted benzaldehyde derivatives. The polarization of the C=N unit of the hydrazone functionality of the heteroaryl derivatives occurs in an analogous manner with that of phenyl derivatives. The electron-withdrawing heteroaryl groups destabilize and the electron-donating groups stabilize the positive charge development at the CN carbon while the effect on the negative charge development is opposite. The 15N NMR chemical shift of the C=N and C=N-N nitrogens and the NBO charges at C=N-N unit can be correlated with the replacement substituent constants of the heteroaryl groups. 13C NMR shifts of the C=N carbon of N,N- dialkylhydrazones of the heteroarenecarbaldehydes can be correlated with a dual parameter equation possessing the polar substituent constant ;* of the heteroaryl group and the electronegativity of the heteroatom as variables.}, language = {en} } @article{HoldtMuellerPotteretal.2006, author = {Holdt, Hans-J{\"u}rgen and M{\"u}ller, Holger and Potter, Matthias and Kelling, Alexandra and Schilde, Uwe and Starke, Ines and Heydenreich, Matthias and Kleinpeter, Erich}, title = {The first sandwich complex with an octa(thioether) coordination sphere : Bis(maleonitrile-tetrathia-12-crown- 4)silver(I)}, issn = {1434-1948}, doi = {10.1002/ejic.200501109}, year = {2006}, abstract = {The new tetrathiacrown ethers maleonitrile-tetrathia-12-crown-4 (mn12S(4)) and maleonitrile-tetrathia-13-crown- 4 (mn13S(4)) have been prepared and characterised by X-ray crystallographic analysis. These crown ethers form 2:1, 3:2 and 1: 1 complexes with AgY (Y = BF4, PF6). The crystal structures of [Ag(mn12S(4))(2)]BF4 (3a), [Ag(mn13S(4))(2)]BF4 (4a) and [Ag-2(mn13S(4))(3)](PF6)(2) (6b) have been determined. Compound 3a contains the centrosymmetric sandwich complex cation [Ag(mn12S(4))(2)](+) where each mn12S(4) ligand is coordinated to the Ag centre in an endo manner through all four S atoms. The 2:1 complex [Ag(mn12S(4))(2)](+) is the first sandwich complex with a tetrathiacrown ether and the first complex with an octa(thioether) coordination sphere. The crystal structure of compound 4a also reveals a 2:1 complex. This complex, [Ag(mnl3S(4))(2)](+), exhibits a half-sandwich structure. One mn13S(4) ligand coordinates to Ag+ by all four S donor atoms and the other 13S(4) crown by only one S atom. Compound 6b contains a dinuclear Ag complex. The Ag complexes 3a,b-8a,b were also studied by electrospray ionisation mass spectrometry. Collision-induced dissociation (CID) was used to compare the relative stability of 2:1 complexes [AgL2]+ and 1:1 complexes [AgL](+) (L = mn12S(4), mn13S(4)). The C-13 NMR chemical shifts of 2:1 and 1:1 Ag complexes and their corresponding free ligands were also estimated and compared. The free energy of the barrier of ring inversion (Delta G(double dagger)) for [Ag(mn12S(4))(2)](+) was determined to be 64 kJmol(-1).}, language = {en} } @article{NeuvonenNeuvonenKochetal.2007, author = {Neuvonen, Helmi and Neuvonen, Kari and Koch, Andreas and Kleinpeter, Erich}, title = {DFT study of the substituent cross-interaction effects on the conformation of substituted N-benzylideneanilines : Models of liquid crystal forming compounds ; use of C-13 Nmr chemcal shift of the C=N carbon as a tool to predict the conformation of the molecule}, doi = {10.1016/j.theochem.2007.03.023}, year = {2007}, abstract = {The conformations of N-benzylideneani lines p-X-C6H4-CH=N-C6H4 p-Y (X, Y = NO2, CN, CF3, F, Cl, Br, H, Me, OMe, NMe2) have been studied by B3LYP density functional (DFT) hybrid method in combination with the 6-31G* or 6-311G* split valence basis set. The twist of the plane of the aniline ring with respect to the other part of the molecule (tau(2)) is systematically controlled by substituents X and Y, the effect of Y being larger. The value of the dihedral angle tau(2), correlates nicely with equation tau(2) = rho(F)(Y)(x)sigma(F)(Y)+rho(+R)(Y)(x)sigma(+)(R)(Y) + k(x) or tau(2) = rho(F)(X)(y)sigma(F)(X)+rho(-)(R)(X)(y)sigma(+)(R)(X) + k(y), respectively, when aniline or benzylidene substituent is varied. ED substituents X diminish the sensitivity of tau(2) to the aniline substituent Y[rho(F)(Y)(x) and rho(+)(R)(Y)(x)] while ED substituents Y increase the sensitivity Of T2 to the benzylidene substituent X[rho(F)(X)(y) and rho(+)(R)(X)(y)]. There seems to be two competitive conjugative interactions for the aniline ring n electrons: one with the nitrogen lone pair and one with the C=N unit. Substituents X and Y adjust the extent of these interactions and therefore the conformation of the molecule. A good correlation is observed between the dihedral angle tau(2) and the experimental C-13 NMR chemical shift of the C=N carbon of N-benzylideneanilines in CDCl3 (C) 2007 Elsevier B.V. All rights reserved.}, language = {en} } @article{HeydenreichKochKlodetal.2006, author = {Heydenreich, Matthias and Koch, Andreas and Klod, Sabrina and Szatmari, Istvan and Fulop, Ferenc and Kleinpeter, Erich}, title = {Synthesis and conformational analysis of naphth[1', 2':5,6][1,3]oxazino[3,2-c][1,3]benzoxazine and naphth[1', 2':5,6][1,3]oxazino[3,4-c][1,3]benzoxazine derivatives}, series = {Tetrahedron}, volume = {62}, journal = {Tetrahedron}, number = {48}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0040-4020}, doi = {10.1016/j.tet.2006.09.037}, pages = {11081 -- 11089}, year = {2006}, abstract = {A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1',2':5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives.}, language = {en} } @article{KleinpeterFettke2008, author = {Kleinpeter, Erich and Fettke, Anja}, title = {Quantification of the (anti)aromaticity of fulvenes subject to ring size}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2008.02.137}, year = {2008}, abstract = {Tria-, penta-, hepta- and nonafulvenes (1-4) have been studied theoretically at the MP2 ab initio level of theory. For the global minimum structures, the occupation of the bonding ;C=C orbital of the exocyclic C=C double bond, obtained by NBO analysis, quantitatively proves ;-electron delocalization which can reveal partial 2-, 6- and 10-;-electron aromaticity, and 4-, 8- and 12-;-electron antiaromaticity of the ring moieties. Beside the corresponding occupation number, this conjugation was quantified by the length of the exocyclic C=C double bond whilst the (anti)aromaticity of the ring moieties of 1-4 was visualized and quantified by through space NMR shielding surfaces (TSNMRS).}, language = {en} } @article{KleinpeterBoelkeFrank2008, author = {Kleinpeter, Erich and B{\"o}lke, Ute and Frank, Andrea}, title = {Polar substituent effect of the ester group on conformational equilibria of O-mono-substituted cyclohexanes{\`u}the para-substituent effect in cyclohexyl benzoates}, doi = {10.1016/j.tet.2008.07.024}, year = {2008}, abstract = {Together with the nonsubstituted reference compound, para-methoxy- and para-nitro cyclohexyl benzoates have been synthesized and their conformational equilibria studied by low temperature NMR spectroscopy and theoretical DFT calculations. The free energy differences ;G° between axial and equatorial conformers were examined with respect to polar substituent influences on the conformational equilibrium of O-mono-substituted cyclohexane.}, language = {en} } @article{HeydenreichKochSzatmarietal.2008, author = {Heydenreich, Matthias and Koch, Andreas and Szatm{\´a}ri, Istv{\´a}n and Fulop, Ferenc and Kleinpeter, Erich}, title = {Synthesis and conformational analysis of naphth[1,2-e][1,3]oxazino[4,3-a][1,3]isoquinoline and naphth[2,1- e][1,3]oxazino[4,3-a]isoquinoline derivatives}, doi = {10.1016/j.tet.2008.05.025}, year = {2008}, abstract = {Through the cyclization of 1-(;-hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline and 1-(;- hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline with formaldehyde, phosgene, p-nitrobenzaldehyde or p-chlorophenyl isothiocyanate, 8-substituted 10,11-dihydro-8H,15bH-naphth[1,2-e][1,3]oxazino[4,3-a]isoquinolines (3 and 4) and 10,11- dihydro-8H,15bH-naphth[2,1-e][1,3]oxazino[4,3-a]isoquinolines (15 and 16) were prepared. Conformational analysis of both the piperidine and the 1,3-oxazine moieties of these heterocycles by NMR spectroscopy and an accompanying theoretical study revealed that these two conformationally flexible six-membered ring moieties prefer twisted chair conformers.}, language = {en} } @article{StarkeFuerstenbergMuelleretal.2006, author = {Starke, Ines and F{\"u}rstenberg, Sylvia and M{\"u}ller, Holger and Holdt, Hans-J{\"u}rgen and Kleinpeter, Erich}, title = {Electrospray mass spectrometric studies of the complexational behavior of maleonitrile thiacrown ethers with various metals}, doi = {10.1002/Rcm.2384}, year = {2006}, abstract = {Electrospray ionization was employed to study the mass spectrometric behavior of the maleonitrile tetrathiacrown ethers mn12S(4) (1) and mn13S(4) (2) and maleonitrile pentathiacrown ether mn15S(5) (3) and of their complexes with various metal salts (MX2, M=Pd, Pt, Ni, Co, Fe; X=Cl, CrCl3, Ni(BF4)(2), TIPF6 or Cd(NO3)(2)) and Cu(SO3CF3)(2). Both singly charged, [MXL](+) and [MXL2]+, and doubly charged complexes, [MLn](2+) (n = 2-5), were observed. The formation of the different complexes consisting of the transition metal ion, the counterion and the various crown ethers and their subsequent dissociation was also studied by collision-induced dissociation measurements which were also used to evaluate the relative stabilities of the complexes. It was found that the collisional voltages for the dissociation of the complexes were generally greater in the [MXL](+) complexes than in the corresponding [MXL2]+ complexes. Copyright (c) 2006 John Wiley \& Sons, Ltd}, language = {en} } @article{KleinpeterSchulenburg2006, author = {Kleinpeter, Erich and Schulenburg, Anja}, title = {Quantification of the push-pull effect in tolanes and a revaluation of the factors affecting the C-13 chemical shifts of the carbon atoms of the C=C triple bond}, issn = {0022-3263}, doi = {10.1021/Jo060199j}, year = {2006}, abstract = {Variously substituted tolanes were employed to show that the push-pull effect is also active in C equivalent to C triple bonds by the successful correlation of the occupation quotient pi*/pi of the pi orbital in resonance with the substituted phenyl moieties of tolanes versus the bond length of the C equivalent to C triple bond. In addition, the influences of the ortho phenyl ring substituents on the C-13 chemical shifts of the triple bond carbon atoms, which were estimated by Rubin et al.(4) to be "inapplicable for describing triple bond polarization", were re-evaluated, leading to the conclusion that, while anisotropic effects of ortho substituents are negligible, the steric ortho-substituent effects do in fact dominate the deviations obtained. A detailed theoretical NBO/NCS study has been employed to illuminate the facts of this case}, language = {en} } @article{KlinkaBalentovaBernatetal.2006, author = {Klinka, Karel D. and Balentova, Eva and Bern{\´a}t, Juraj and Imrich, Jan and Vavrusova, Martina and Kleinpeter, Erich and Pihlaja, Kalevi and Koch, Andreas}, title = {Tautomerism, regioisomerism, and cyclization reactions of acridinyl thiosemicarbazides}, issn = {0022-152X}, doi = {10.1002/jhet.5570430317}, year = {2006}, abstract = {The regioselectivities of methyl- and phenylhydrazine with acridin-9-yl isothiocyanate (thus yielding thiosemicarbazides with acridine substituted on the urea-type side) were examined. Methythydrazine regioselectivity was high with the alpha-nitrogen atom overwhelmingly more nucleophilic than the beta-nitrogen atom; phenylhydrazine regioselectivity was poor but varied with the solvent and only in the case of ethanol was nucleophilic predominance of the alpha-nitrogen atom pronounced. Of note, whilst both phenyl thiosemicarbazides were present in solution only as spiro forms, the methyl product was present as an equilibrium mixture of open-chain and spiro thiosemicarbazides. Reactions on the NH2 blocked analogue of methyl acridin-9-ylthiosemicarbazide (1-isopropylidene-2- methylthiosemicarbazide) were also examined. Interestingly, present in the starting material itself was a structural motif of novelty wherein a triazolethione represented the major species of an equilibrium between cyclic and open-chain forms}, language = {en} } @article{SchildeErkKleinpeter2006, author = {Schilde, Uwe and Erk, {\c{C}}akil and Kleinpeter, Erich}, title = {The crystal and molecular structures of sodium and barium complexes of dibenzo-24-crown-8 ether}, doi = {10.1524/zkri.2006.221.3.231}, year = {2006}, abstract = {The sodium and barium isothiocyanate complexes of 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenzo[b,n]- 1,4,7,10,13,16,19,22-octaoxacyclotetracosin (dibenzo-24-crown-8 ether = DB24C8) were synthesized and analyzed by X-ray diffraction. The sodium complex, [Na(DB24C8)(NCS)(H2O)] 1, crystallizes in the orthorhombic space group Fdd2 with 16 molecules in the unit cell. The coordination number of Na is 6 and the central ion is located in a distorted octahedric environment. Only four of the crown ether oxygen atoms are involved. The coordination polyhedron is completed by the isothiocanate anion and by a water molecule, which is stabilized by hydrogen bonds. The barium complex, [Ba(DB24C8)(NCS)(2)] 2, crystallizes in the trigonale space group P3(1)21 with 3 molecules in the unit cell. Crystallographic C-2 symmetry is observed for the complex. The coordination number of Ba is 10. Barium is coordinated with the eight oxygen atoms of the macrocyclic ligand and with two isothiocyanate anions. The absolute structure was estimated using the FLACK parameter}, language = {en} } @article{KammKammSchmidtetal.2006, author = {Kamm, Birgit and Kamm, Michael and Schmidt, Matthias and Starke, Ines and Kleinpeter, Erich}, title = {Chemical and biochemical generation of carbohydrates from lignocellulose-feedstock (Lupinus nootkatensis) : quantification of glucose}, issn = {0045-6535}, doi = {10.1016/j.chemosphere.2005.03.073}, year = {2006}, abstract = {Different chemical and enzymatic methods were applied for the hydrolysis of main stems from Lupinus nootkatensis (harvest November 2002). The whole process (all steps) is based on the lignocellulose-feedstock biorefinery regime. The acid hydrolysis of L. was performed with concentrated hydrochloric acid; advantages in this process are exothermic hydrolysis and the possibility of acid recovery. Enzymatic hydrolysis achieved high yields of fermentable carbohydrates (regarding to input cellulose) with high selectivity. However, this way requires the generation of cellulose from L. by chemical pulping. Monosaccharide derivatives thus obtained were identified by their GC retention times and the corresponding MS fragmentation. Hexamethyldisilazane was used as derivatization reagent to prepare the trimethylsilyl derivatives of the carbohydrates and of the degradations products of cellulose from the different fractions. The glucose content was quantified by GC peak integration with respect to an internal standard.}, language = {en} } @article{RasovicSteelKleinpeteretal.2007, author = {Rasovic, Aleksandar and Steel, Peter J. and Kleinpeter, Erich and Markovic, Rade}, title = {Regioselective synthesis of 1,3-thiazines by sequential 4-oxothiazolidine to 1,2-dithiole to 1,3-thiazine transformations : role of intramolecular non-bonded S...O interactions}, doi = {10.1016/j.tet.2006.12.075}, year = {2007}, abstract = {A new synthetic approach to 2,3-dihydro-4H-1,3-thiazine derivatives based upon reductive rearrangement of 1,2- dithiole-3-ylidene thiones has been developed. In turn, the 1,2-dithiole derivatives were prepared by an efficient ring- opening-closing process of 2-alkylidene-4-oxothiazolidines, induced in the presence of Lawesson's reagent by intramolecular non-bonded 1,5-type S...O interactions in the 4-oxothiazolidine precursors.}, language = {en} } @article{KleinpeterRollaKochetal.2006, author = {Kleinpeter, Erich and Rolla, Nadja and Koch, Andreas and Taddei, Fernando}, title = {Hyperconjugation and the increasing bulk of OCOCX3 substituents in trans-1,4-disubstituted cyclohexanes destabilize the diequatorial conformer}, issn = {4393-4399}, doi = {10.1021/Jo0600858}, year = {2006}, abstract = {The trans diesters of 1,4-cyclohexanediol with a number of acetic acid analogues, CX3COOH, of varying steric hindrance and polarity (CX3 = Me, Et, iso-Pr, tert-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, CBr3) were synthesized, and the axial, axial/equatorial, equatorial conformational equilibria were studied by low-temperature H-1 NMR spectroscopy in CD2Cl2. The structures and relative energies of the axial, axial and equatorial, equatorial conformers were calculated at both the MP2/6-311G* and the MP2/6-311+G* levels of theory, and it was only by including diffuse functions that a good correlation of Delta G degrees(calcd) vs Delta G(exptl) could be obtained. Both the structures and the energy differences of the axial, axial and equatorial, equatorial conformers are discussed with respect to the established models of conformational analysis, viz., steric 1,3-diaxial and hyperconjugative interactions. Interestingly, the hyperconjugative interactions sigma(C-C)/sigma(C-H)->sigma*(C-O), together with a steric effect which also destabilizes the equatorial, equatorial conformers on increasing bulk of the substituents, proved to dominate the position of the conformational equilibria. In addition, the preference of the axial, axial conformers with respect to their equatorial, equatorial analogues was greater than expected from the conformational energies of the corresponding substituents in the monosubstituted cyclohexyl esters. The reason for this very interesting and unexpected result is also discussed}, language = {en} } @article{YonedaLealSeidletal.2007, author = {Yoneda, Julliane Diniz and Leal, Katia Zaccur and Seidl, Peter Rudolf and Azeredo, Rodrigo Bagueira de V. and Kleinpeter, Erich}, title = {Camphor : a good model for illustrating NMR techniques}, year = {2007}, abstract = {CAMPHOR: A GOOD MODEL FOR ILLUSTRATING NMR TECHNIQUES. The use of Nuclear Magnetic Resonance spectroscopy to establish the three-dimensional structures of molecules is an important component of modern Chemistry courses. The combination of techniques that can be used for this purpose is conveniently illustrated by their application to the camphor molecule. This paper presents applications of several techniques used in NMR spectral interpretation in an increasing order of complexity. The result of individual experiments is illustrated in order to familiarize the user with the way connectivity through bonds and through space is established from 1D/2D-NMR spectra and molecular stereochemistry is determined from different NMR experiments}, language = {en} } @article{ModarresiAlamKhamooshiRostamizadehetal.2007, author = {Modarresi-Alam, Ali Reza and Khamooshi, Ferydoon and Rostamizadeh, Mohsen and Keykha, Hossein and Nasrollahzahdeh, Mahmoud and Bijanzadeh, Hamid-Reza and Kleinpeter, Erich}, title = {Dynamic 1H NMR spectroscopic study of the restricted S-N rotation in aryl-N-(arylsulfonyl)-N- (triphenylphosphoranylidene)imidocarbamates}, year = {2007}, abstract = {Dynamic 1H NMR (500 MHz) investigation of aryl-N-(arylsulfonyl)-N-(triphenylphosphoranylidene)imidocarbamates in CDCl3, CD3COCD3, and CD3OD at the temperature range of 183-298 K is reported. The observed free energy barriers (almost 12 kcal mol;1) are attributed to conformational isomerization about the N{\`u}S bond and these barriers show very little solvent dependence.}, language = {en} } @article{ModarresiNajafiRostamizadehetal.2007, author = {Modarresi, Ali Reza and Najafi, Parisa and Rostamizadeh, Mohsen and Keykha, Hossein and Bijanzadeh, Hamid-Reza and Kleinpeter, Erich}, title = {Dynamic 1H NMR study of the barrier to rotation about the C-N bond in primary carbamates and its solvent dependence}, year = {2007}, abstract = {The dynamic 1H NMR study of some primary carbamates in the solvents CDCl3 and CD3COCD3 between 183 and 298 K is reported. The free energies of activation, thus obtained (12.4 to 14.3 kcal mol-1), were attributed to the conformational isomerization about the N-C bond. These barriers to rotation show solvent dependence in contrast to the tertiary analogues and are lower in free energy by ca. 2-3 kcal mol-1.}, language = {en} } @article{KleinpeterStamboliyska2008, author = {Kleinpeter, Erich and Stamboliyska, Bistra A.}, title = {Quantification of the Push-Pull Character of Donor-Acceptor Triazenes}, doi = {10.1021/Jo8013758}, year = {2008}, abstract = {The Push-pull character of two series of donor-acceptor triazenes has been quantified by C-13 and N-15 chemical shift differences of the partial N(1)=N(2) and N(3)=C(4) double bonds in the central linking C=N-N=N-C unit and by the quotient of the occupations of both the bonding pi and antibonding orbitals pi* of these partial double bonds. Excellent correlations of the two estimates, to quantify the push-pull effect, with the bond lengths strongly recommend the occupation quotients pi*/pi, the N-15 chemical shift differences Delta delta[N(l),N(2)], and the corresponding bond lengths as reasonable sensors for quantifying charge alternation along the C=N-N=N-C linking unit, for the donor- acceptor quality of the triazenes 1 and 2 and for the molecular hyperpolarizability beta(0) of these compounds. Within this context, certain Substances can be strongly recommended for NLO application.}, language = {en} } @article{KlikaKramerKleinpeter2009, author = {Klika, Karel D. and Kramer, Markus and Kleinpeter, Erich}, title = {DFT computational studies of hydrogen bonding-based diastereomeric complexes : limitations and applications to enantiodifferentiation}, issn = {0166-1280}, doi = {10.1016/j.theochem.2009.08.003}, year = {2009}, abstract = {Molecular modeling calculations using DFT at the B3LYP/6-31G(d,p) level of theory have been performed on diastereomeric complexes formed between chiral carboxylate anions and chiral urea receptors, a combination previously demonstrated to enable enantiodifferentiation by electrochemical sensing. The calculations correctly predicted the stability order of the enantiomers in acetonitrile solution when the distinction between the enantiomers was above the declared threshold reliability value of 1 kcal mol;1 for computations at this level of theory. Thus, the calculations can not only be applied to predict the likely success of undertakings using the analytical method, it can also, provided ;E is sufficient, potentially be used to determine the absolute configuration of chiral analytes with at least the racemate in hand. The previously successful enantiodifferentiations of various amino acids and alcohols using chiral ion mobility spectroscopy (CIMS) with (S)-2-butanol as the chiral selector were also evaluated by DFT calculations. The calculations again correctly predicted the stability order of the enantiomers when the calculated ;E was above the threshold value though cases not providing a value for ;E above the threshold value was problematic for this system. Attempts to address this shortcoming included an expanded conformational evaluation, a broader analytical approach, and an extended basis set.}, language = {en} } @article{ShainyanUshakovMeshcheryakovetal.2008, author = {Shainyan, Bagrat A. and Ushakov, Igor A. and Meshcheryakov, Vladimir I. and Koch, Andreas and Kleinpeter, Erich}, title = {Variable temperature NMR and theoretical study of the stereodynamics of 5-trifluoromethylsulfonyl-1,3,5- dioxaazinane : Perlin effect subject to heteroatom substitution}, year = {2008}, abstract = {Multinuclear dynamic NMR spectroscopy of 5-trifluoromethylsulfonyl-1,3,5-dioxaazinane (4) revealed the existence of two close in energy chair conformers with differently oriented CF3 groups with respect to the ring. Of the two alternative routes for their interconversion, the ring inversion path with intermediate formation of the corresponding 2,5-twist-conformer is preferred, with the energy barrier of 11.2 kcal/mol in excellent agreement with the experimental value (11.7 kcal/mol). The Perlin effect is studied experimentally and calculated theoretically for all CH2 groups and found to be subject to the nature of the adjacent heteroatoms O and N, respectively.}, language = {en} } @article{KleinpeterKochShainyan2008, author = {Kleinpeter, Erich and Koch, Andreas and Shainyan, Bagrat A.}, title = {Cyclobutadiene dianion derivatives : Planar 4c,6e or three-dimensional 6c,6e aromaticity?}, doi = {10.1016/j.theochem.2008.05.027}, year = {2008}, abstract = {The spatial magnetic properties (Through Space NMR Shieldings - TSNMRS) of two cyclobutadiene derivatives (2 and 5) and of a number of cyclobutadiene dianion derivatives (3, 4 and 6-8) have been calculated by the GIAO perturbation method employing the Nucleus-Independent Chemical Shift (NICS) concept of P. v. Ragu{\´e} Schleyer, and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various size and direction. TSNMRS values can be successfully employed to quantify and visualize the (anti)aromaticity of the compounds studied and to discuss the influence of Li+ complexation to cyclobutadiene dianion (4a, 7 and 8) on planar 4c,6e or three-dimensional 6c,6e aromaticity.}, language = {en} } @article{BaranacStojanovicTatarKleinpeteretal.2008, author = {Baranac-Stojanovic, Marija and Tatar, Jovanan and Kleinpeter, Erich and Markovic, Rade}, title = {High-Yield Synthesis of Substituted and Unsubstituted Pyridinium Salts Containing a 4-Oxothiazolidine Moiety}, year = {2008}, abstract = {A new series of unsubstituted and substituted pyridinium salts bearing a 4-oxothiazolidinyl moiety has been prepared by an efficient rearrangement of 2-(1-bromoalkylidene)thiazolidin-4-ones. The process in based on three steps, namely carbon-bromine cleavage, bromine transfer, and substitution, each induced by pyridine or its derivatives, acting as base and reactant.}, language = {en} } @article{ShainyanUshakovTolstikovaetal.2008, author = {Shainyan, Bagrat A. and Ushakov, Igor A. and Tolstikova, Ljudmila L. and Koch, Andreas and Kleinpeter, Erich}, title = {N-Trifyl substituted 1,4-diheterocyclohexanes{\`u}stereodynamics and the Perlin effect}, year = {2008}, abstract = {The stereodynamic behaviour of 1-(trifluoromethylsulfonyl)piperidine 1, 4-(trifluoromethylsulfonyl)morpholine 2, 1,4-bis(trifluoromethylsulfonyl)piperazine 3 and 4-(trifluoromethylsulfonyl)thiomorpholine 1,1-dioxide 4 was studied by low-temperature 1H, 13C and 19F NMR spectroscopies. In acetone solution, compounds 1, 2 and 4 were found to exist as mixtures of two conformers in the ratio of 4:1, 4:1 and 8:1, respectively, differing by orientation of the CF3 group with respect to the ring. Compound 3 exists as a mixture of three conformers in the ratio of 3:28:69 also differing by the orientation of the two CF3 groups. Unlike the previously studied N-trifyl substituted 1,3,5-triheterocyclohexanes, the preferred conformers of compound 1 and of 1,4-diheterocyclohexanes 2-4 are those with the CF3 group directed outward from the ring, which is caused by intramolecular interactions of the oxygen atoms of the CF3SO2N groups with the equatorial hydrogens in the ;-position. B3LYP/6-311+G(d,p) calculations of the energy, geometry and NMR parameters corroborate the experimental data. The calculated Perlin effects for all conformers of compounds 1-4 as well as those measured for the major conformers of compounds 3 and 4 were analyzed by the use of the NBO analysis.}, language = {en} } @article{KleinpeterKoch2008, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Trisannelated benzenes - Aromatic molecules or 1,3,5-cyclohexatriene derivatives subjected to magnetic properties}, doi = {10.1016/j.theochem.2008.02.013}, year = {2008}, abstract = {The through space NMR shielding (TSNMRS) values of two tricyclobutabenzene (TCBB) derivatives 2, of the corresponding hexamethylene and hexaoxo TCBB derivatives 3, of [4n]annuleno[4n + 2]annulene 5 and of its tricyclobutadiene parent compound 4 have been ab initio calculated by the GIAO perturbation method employing the nucleus- independent chemical shift (NICS) concept of Paul von Ragu{\´e} Schleyer, and visualized as iso-chemical shielding surfaces (ICSS). TSNMRS values can be successfully employed to quantify and visualize the aromaticity of the central, and in 5 also of the terminal benzene ring moieties.}, language = {en} } @article{StarkeSchusterFulopetal.2008, author = {Starke, Ines and Schuster, Ildikk{\´o} and Fulop, Ferenc and Kleinpeter, Erich}, title = {Mass spectra of tetrahydroisoquinoline-fused 1,3,2-O,N,P- and 1,2,3-O,S,N-heterocycles: influence of ring size and fusion, of present heteroatoms, substituent effects and of the stereochemistry on fra}, year = {2008}, abstract = {The electron ionization (EI) mass spectra of a variety of stereoisomeric tricyclic 1,3,2-oxazaphosphino[4,3- a]isoquinolines (1-4), 1,2,3-oxathiazino[4,3-a]isoquinoline-4-oxides (5-7) and the -4,4-dioxides (8-10) of oxazaphospholo- and oxathiazolo[4,3-a]- (11, 12, 15 and 16) and -[3,4-b]isoquinolines (13, 14 and 17) were recorded. Ring size and fusion, the different heteroatoms (P and S) and substituents on the ring systems strongly influence the mass spectra. In addition, mass spectra of the stereoisomers of compounds 1, 2 and 13, 14 revealed stereochemically relevant differences which are not observed for the other pairs of isomers. Copyright © 2008 John Wiley \& Sons, Ltd.}, language = {en} } @article{SchusterKochHeydenreichetal.2008, author = {Schuster, Ildik{\´o} and Koch, Andreas and Heydenreich, Matthias and Kleinpeter, Erich and Forr{\´o}, Enik{\"o} and L{\´a}z{\´a}r, L{\´a}szl{\´o} and Sillanp{\"a}{\"a}, Reijo and Fulop, Ferenc}, title = {Synthesis and Conformational Analysis of Tetrahydroisoquinoline-Fused 1,3,2-Oxazaphospholidines and 1,2,3- Oxathiazolidines}, year = {2008}, abstract = {The cyclizations of tetrahydroisoquinoline 1,2-amino alcohols with phenylphosphonic dichloride, bis(2- chloroethyl)phosphoramidic dichloride, thionyl chloride and sulfuryl chloride were utilized to synthesize 1,5,6,10b- tetrahydro-1,3,2-oxazaphospholo[4,3-a]isoquinolines (2, 3), 1,5,10,10a-tetrahydro-1,3,2-oxazaphospholo[3,4- b]isoquinolines (8, 9), 1,5,6,10b-tetrahydro-1,2,3-oxathiazolo[4,3-a]isoquinolines (4-6) anda 1,5,10,10a-tetrahydro- 1,2,3-oxathiazolo[3,4-b]isoquinoline (11), which are the first representatives of these ring systems. NMR spectroscopic analysis revealed the existence of conformational equilibria that are fast on the NMR timescale. Theoretical DFT calculations pointed to the participation of generally two preferred conformers in the conformational equilibria; the positions of the equilibria were indicated by the experimental NMR spectroscopic parameters, and they are in good agreement with the theoretically calculated energy differences of the participating conformers. For two compounds, which could be not isolated (10, 12), both the preferred conformers and the stereochemistry could be concluded from the DFT calculation results.}, language = {en} } @article{StarkeKammerGrunwaldetal.2008, author = {Starke, Ines and Kammer, Stefan and Grunwald, Nicolas and Schilde, Uwe and Holdt, Hans-J{\"u}rgen and Kleinpeter, Erich}, title = {Complexation of diazaperylene and bisisoquinoline with transition metal ions in the gas phase studied by electrospray ionization mass spectrometry}, year = {2008}, abstract = {The complex formation of the ligands 1,12-diazaperylene (dap), 1,1-bisisoquinoline (bis), 2,2-bipyridine (bpy) and 1,10-phenanthroline (phen) with transition metal ions (M = Fe, Co, Ni, Cu, Zn, Ru, Os, Re, Pd, Pt, Ag and Cd) in the gas phase has been studied by electrospray ionization mass spectrometry. With the exception of Ru, Os, Fe, Ni and Cu, singly charged complexes [MLn]+ (n = 1,2) were observed. The complexes of dap and bis with Ru, Os, Fe and Ni ions, and the mixed ligand complexes with bpy and phen, are preferably of the doubly charged type [ML3]2+. In addition, collision- induced dissociation (CID) measurements were employed to evaluate the relative stabilities of these complexes. The CID experiments of mixed-ligand complexes which contain both dap and phen or dap and bpy exhibit preferential elimination of bpy, indicating that bpy is a weaker ligand than phen and dap.}, language = {en} } @article{Kleinpeter2008, author = {Kleinpeter, Erich}, title = {Quantitative study and visualization of spherical 2(N + 1)2 homoaromaticity by through space NMR shieldings (TSNMRS)}, doi = {10.1016/j.theochem.2007.11.029}, year = {2008}, abstract = {The through space NMR shielding (TSNMRS) values of adamantane, the 2(N + 1)2 spherical (4c, 2e) homoaromatic compounds 1,3-dehydro-5,7-adamantandiyl dication (C10H122+) and 1,3-dehydro-5,7-cubandiyl dication (C8H42+), and the (6c, 8e) homoaromatic compound 2,2;,4,4;,6,6;,8,8;,10,10;-dehydroadamantane tetracation (C10H44+) have been ab initio calculated, employing the NICS concept, and visualized as iso-chemical shielding surfaces (ICSSs). TSNMRS values can be successfully employed to study both the endohedral and exohedral aromaticity/ antiaromaticity of the compounds studied.}, language = {en} }