@article{KleinpeterKoch2023, author = {Kleinpeter, Erich and Koch, Andreas}, title = {The multiple bond character of the carbon-boron bond in boron trapped N-heterocyclic carbenes (NHCs) and cyclic(alkyl)(amino) carbenes (CAACs) on the magnetic criterion}, series = {Tetrahedron}, volume = {140}, journal = {Tetrahedron}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2023.133469}, pages = {13}, year = {2023}, abstract = {Geometry, 11B, 13C chemical shifts and the spatial magnetic properties (Through-Space NMR Shieldings -TSNMRS) of both cations and anions of boron-trapped N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) and of the corresponding diborane/diborene/diboryne dis-carbene adducts have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept; the TSNMRS results are visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The ICSS of the TSNMRS (actually the anisotropy effects measurable in 1H NMR spectroscopy) are employed to qualify and quantify the present multiple bond character of the Carbene-Boron bond in the trapped NHCs and CAACs. Results are confirmed by bond length and 11B/13C chemical shift variations. Thus the partial multiple bond character of the Carbene-Boron bond cannot be expressed by the arrow of weak, much longer dative bonds and should be omitted as in other covalent lone pair-it or triel bonds. \& COPY; 2023 Elsevier Ltd. All rights reserved.}, language = {en} } @article{KleinpeterKoch2022, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Cyclazines-structure and aromaticity or antiaromaticity on the magnetic criterion}, series = {European journal of organic chemistry}, volume = {2022}, journal = {European journal of organic chemistry}, number = {8}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.202101362}, pages = {12}, year = {2022}, abstract = {Structure and spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of all ten cycl[2.2.2]azine to cycl[4.4.4]azine, hetero-analogues and the corresponding hydrocarbons have been calculated at the B3LYP/6-311G(d,p) theory level using the GIAO perturbation method and employing the nucleus independent chemical shift (NICS) concept. The TSNMRS values (actually, the ring current effect as measurable in H-1 NMR spectroscopy) are visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction, and employed to readily qualify and quantify the degree of (anti)aromaticity. Results are confirmed by NMR [delta(H-1)/ppm, delta(N-15)/ppm] and geometry (planar, twisted, bow-shaped) data. The cyclazines N[2.2.2](-) up to N[2.4.4](-) are planar or at most slightly bowl-shaped and, due to coherent peripheral ring currents (except in N[2.3.3](-), N[2.3.4], N[3.3.4](+) and N[2.4.4](+)), develop aromaticity or anti-aromaticity of the whole molecules dependent on the number of peripheral conjugated pi electrons. The cyclazines N[2.3.3](-), N[2.3.4], N[3.3.4](+) and N[2.4.4](+) develop two ring currents of different direction within the same molecule, in which the dominating ring current proves to be paratropic (in N[3.3.4](+) diatropic) including the nodal N p(z) lone pair into the conjugation. The residual cyclazines N[3.4.4], N[4.4.4](-) and N[4.4.4](+) are heavily twisted and, therefore, are not developing peripheral or diverse ring currents. The TSNMRS information about cyclazines and the parent tricyclic annulene analogues is congruent subject to structure and number of peripheral or internal conjugated pi electrons, the corresponding (anti)aromaticity is in unequivocal accordance with Huckel's rule.}, language = {en} } @article{KleinpeterKoch2021, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Intramolecular carbene stabilization via 3c,2e bonding on basis of the magnetic criterion}, series = {Tetrahedron : the international journal for the rapid publication of full original research papers and critical reviews in organic chemistry}, volume = {95}, journal = {Tetrahedron : the international journal for the rapid publication of full original research papers and critical reviews in organic chemistry}, publisher = {Elsevier Science}, address = {Amsterdam}, issn = {0040-4020}, doi = {10.1016/j.tet.2021.132357}, pages = {9}, year = {2021}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent cyclobutylcarbene 8, 1,2-diboretane-3-ylidene 9, and some carbene analogues of boron 14-18 as most intriguing examples of carbenes, which can be stabilized as homoaromatic systems with 3c,2e bonding, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually, ring current effect/anisotropy effects as measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the degree of present 3c,2e-homoaromaticity. Results are confirmed by geometry (bond angles and bond lengths) and spectroscopic data, the delta(B-11)/ppm data and the C-13 chemical shifts of the carbene electron-deficient centre.}, language = {en} } @article{BuyinzaDereseNdakalaetal.2021, author = {Buyinza, Daniel and Derese, Solomon and Ndakala, Albert and Heydenreich, Matthias and Yenesew, Abiy and Koch, Andreas and Oriko, Richard}, title = {A coumestan and a coumaronochromone from Millettia lasiantha}, series = {Biochemical systematics and ecology}, volume = {97}, journal = {Biochemical systematics and ecology}, publisher = {Elsevier}, address = {Oxford}, issn = {0305-1978}, doi = {10.1016/j.bse.2021.104277}, pages = {5}, year = {2021}, abstract = {The manuscript describes the phytochemical investigation of the roots, leaves and stem bark of Millettia lasiantha resulting in the isolation of twelve compounds including two new isomeric isoflavones lascoumestan and las-coumaronochromone. The structures of the new compounds were determined using different spectroscopic techniques.}, language = {en} } @article{KleinpeterKoch2021, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Dative or coordinative carbon-boron bond in boron trapped N-heterocyclic carbenes (NHCs)?}, series = {Tetrahedron : the international journal for the rapid publication of full original research papers and critical reviews in organic chemistry}, volume = {80}, journal = {Tetrahedron : the international journal for the rapid publication of full original research papers and critical reviews in organic chemistry}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0040-4020}, doi = {10.1016/j.tet.2020.131787}, pages = {8}, year = {2021}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of isolated as well as B-C bond length varied model compounds (BR3 trapped NHCs) have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the present dative vs. coordinative bond character of the boron-carbon bond in the trapped NHCs. Results are confirmed by bond lengths and B-11/C-13 chemical shift variations in the BR3 trapped NHCs.}, language = {en} } @article{KleinpeterKoch2021, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Quantification of sigma-acceptor and pi-donor stabilization in O, S and Hal analogues of N-heterocyclic carbenes (NHCs) on the magnetic criterion}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {125}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, number = {33}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.1c05257}, pages = {7235 -- 7245}, year = {2021}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.}, language = {en} } @article{KleinpeterKoch2020, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Bent Allenes or Di-1,3-betaines-An Answer Given on the Magnetic Criterion}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {124}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, number = {16}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.0c01392}, pages = {3180 -- 3190}, year = {2020}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent allene 1, the corresponding C-extended 1,3-butadiene derivative 2, and a number of related compounds 3 -20 have been calculated using the gauge-independent atomic orbital perturbation method, employing the nucleus-independent chemical shift concept and visualized as isochemical shielding surfaces of various sizes and directions. Prior to that, both structures and C-13 chemical shifts were calculated and compared with available experimental bond lengths and delta(C-13)/ppm values (also, as a quality criterion for the computed structures). Bond lengths, the delta(C-13)/ppm, and the TSNMRS values are employed to qualify and quantify the electronic structure of the studied compounds in terms of dative or classical electron-sharing bonds.}, language = {en} } @article{BelasriTopalHeydenreichetal.2020, author = {Belasri, Khadija and Topal, Leila and Heydenreich, Matthias and Koch, Andreas and Kleinpeter, Erich and Fulop, Ferenc and Szatmari, Istvan}, title = {Synthesis and conformational analysis of naphthoxazine-fused phenanthrene derivatives}, series = {Molecules}, volume = {25}, journal = {Molecules}, number = {11}, publisher = {MDPI}, address = {Basel}, issn = {1420-3049}, doi = {10.3390/molecules25112524}, pages = {15}, year = {2020}, abstract = {The synthesis of new phenanthr[9,10-e][1,3]oxazines was achieved by the direct coupling of 9-phenanthrol with cyclic imines in the modified aza-Friedel-Crafts reaction followed by the ring closure of the resulting bifunctional aminophenanthrols with formaldehyde. Aminophenanthrol-type Mannich bases were synthesised and transformed to phenanthr[9,10-e][1,3]oxazines via [4 + 2] cycloaddition. Detailed NMR structural analyses of the new polyheterocycles as well as conformational studies including Density Functional Theory (DFT) modelling were performed. The relative stability of ortho-quinone methides (o-QMs) was calculated, the geometries obtained were compared with the experimentally determined NMR structures, and thereby, the regioselectivity of the reactions has been assigned.}, language = {en} } @article{KochStamboliyskaMikhovaetal.2019, author = {Koch, Andreas and Stamboliyska, Bistra and Mikhova, Bozhana and Breznica-Selmani, Pranvera and Mladenovska, Kristina and Popovski, Emil}, title = {Calculations of C-13 NMR chemical shifts and F-C coupling constants of ciprofloxacin}, series = {Magnetic resonance in chemistry}, volume = {57}, journal = {Magnetic resonance in chemistry}, number = {4}, publisher = {Wiley}, address = {Hoboken}, issn = {0749-1581}, doi = {10.1002/mrc.4827}, pages = {75 -- 84}, year = {2019}, abstract = {Ciprofloxacin is a widely used fluoroquinolone antibiotic. In this work, a comprehensive evaluation of MP2 and DFT with different functionals and basis sets was carried out to select the most suitable level of theory for the study of the NMR properties of ciprofloxacin. Their relative predictive capabilities were evaluated comparing the theoretically predicted and experimental spectral data. Our computational results indicated that in contrast to the solid state, the molecule of ciprofloxacin does not exist as a zwitterion in gaseous state. The results of the calculations of the chemical shifts most close to the experimental were obtained with B3LYP/aug-cc-pVDZ. The F-C coupling constants were calculated systematically with different DFT methods and several basis sets. In general, the calculations of the coupling constants with the BHandH computational method including the applied in this work 6-311++G**, EPRII, and EPRIII basis sets showed a good reproducibility of the experimental values of the coupling constants.}, language = {en} } @article{KleinpeterKoch2019, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Is the term "Carbene" justified for remote N-heterocyclic carbenes (r-NHCs) and abnormal N-heterocyclic carbenes (aNHCs/MICs)?}, series = {Tetrahedron}, volume = {75}, journal = {Tetrahedron}, number = {11}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2019.02.005}, pages = {1548 -- 1554}, year = {2019}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of typical N-heterocyclic carbenes NHCs, r-NHCs, a-NHCs and MICs have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. Prior to that both structures and 13C chemical shifts were calculated and in case of isolated carbenes the computed δ(13C)/ppm values compared (as a quality criterion for obtained structures) with the experimental ones. The TSNMRS values of the studied carbenes, which are in mesomeric equilibrium with zwitterionic (ylide/betaine/mesoionic) resonance contributors, are employed to qualify and quantify the present electronic structure and if the term carbene is still justified to denote the compounds studied. The results, thus obtained from spatial magnetic properties (TSNMRS), are compared with the geometry of the compounds, the corresponding WIBERG's bond index values, and the 13C chemical shifts especially of the carbene electron-deficient centre.}, language = {en} }