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GROUP IX.
APPLICATION OF OPTICAL AND NMR SPECTROSCOPIES IN ELUCIDATION OF THE STRUCTURE OF ORGANIC COMPOUNDS, MOLECULAR INTERACTIONS IN SOLUTIONS

Head of the group

Prof. Krystyna Kamieńska-Trela

 e-mail: <kkt@icho.edu.pl>

Ph.D., 1967, Institute of Organic Chemistry PAS.

Post-doc, Fredericton University, NB, Canada, 1968/1969, Alexander von Humboldt Foundation Fellow, Georg-August University, Göttingen, 1976/1978.

Habilitation, 1982, Institute of Organic Chemistry PAS.

Full Professor, 1996.

Award of the Secretary of the III Division of PAS, 1982.

Award of the Ministry of Science, High Education and Technique, 1974.

Staff:

Prof. Michał Witanowski (professor emeritus), Magdalena Bechcicka, techn.; Zenobia Biedrzycka Ph.D., Marta Bugaj, Ph.D. student, Andrzej Dąbrowski, Ph.D., Lidia Kania, Ph.D., Hanna Sokół, techn.

Research activity:

The studies carried out in our group are devoted to structural analysis of a variety of organic compounds. This includes heterocyclic five- and six-membered heterocycles with special attention paid to Li, Mg, Cd and F derivatives, bi- and tetracyclic heterocyclic systems, quinolizines, enaminoketones and their fluoro derivatives, substituted acetylenes and some important biological systems such as guanine and related nucleozides and nucleotides. Modern NMR techniques, FT IR, UV and dipole moment measurements, as well as theoretical calculations are applied.

Especially interesting information follows from an analysis of both the experimental and theoretical spin-spin coupling constants across one and more bonds. Among others an analysis of experimentally determined and DFT calculated 1JCC couplings  obtained for a very large group of thiophenes, furans, pyrroles, pyridines and their N-oxides has shown that this parameter can be used as a measure of aromaticity of the heterocycles systems studied. It has been also of great interest noting that 1JCC vs Ex relationship (Ex electronegativity of substituent) is linear in the case of acetylenes and ethylenes, and logarithmic in the case of  aromatic systems. A rough linear correlation has been found between the ln 1JCºC(DFT) couplings and the DFT optimized bond lengths, rCºC.

One of the most interesting results obtained by us recently concerns  concentration and temperature dependent IR, NMR and dipole moment studies performed for 4-N,N-dimethylamino-1,1,1-trifluoro-3-buten-2-one and its two higher analogues. We have shown that these compounds undergo, in non-polar solvents, a reversible dimerization process, during which  hydrogen bond formation between the olefinic hydrogens H(4) and the oxygen atom of the carbonyl groups takes place. The dimers are “closed” with two hydrogen bonds in a 10-membered ring. Quantitative analysis of the 1H NMR data yielded ΔH0 = - 4.2 kcal mol-1 and ΔS0 = - 11.2 cal deg-1 mol-1 per one hydrogen bond. This is the strongest intermolecular hydrogen bond involving a C-H donor and the first intermolecular one reported in the literature.

General problems of nitrogen (14N and 15N) NMR and applications thereof in organic chemistry are pursued. Attention is paid to nitrogen NMR shieldings of chemical shifts as a function of molecular interactions and electron charge distribution, to precise calibration and referencing procedures for nitrogen magnetic shieldings, and to quantum-mechanical calculations of the shieldings, including various degrees of sophistication within both semi-empirical and DFT/ab initio methods. Generalized accounts of nitrogen NMR are regularly presented with a view to introduce the unification of nitrogen chemical shift scales.

Selected scientific publications:

  1. K. Kamieńska-Trela, Jacek Wójcik, Applications of Spin-Spin Coupling Constants, Specialist Periodical Reports, NMR, ed. G.A. Webb, The Royal Society of Chemistry,   London, 29 (2000), 30 (2001), 31 (2002), 32, (2003), 33 (2004).

  2. J. Wójcik, K. Kamieńska-Trela, M. Pecul, E. Bartoszak-Adamska, S. I. Vdovienko, I.I.    Gerus, Improper Hydrogen C-H···O Bonds Cause Self-Association of a,b- Enaminoketones    Containing Fluorosubstituted Alkyl Group, ChemPhysChem, 5, 100 (2004).

  3. M. Wandas, A. Puszko, Z. Biedrzycka, M. Witanowski, Nitrogen NMR shieldings of some nitro derivatives of 2-amino-4-methylpyridine systems, Khim. Geterotsikl. Soed., 873,  (2004).

  4. M. Witanowski, Z. Biedrzycka, W. Sicińska, Z. Grabowski, A study of solvent polarity and hydrogen bonding effects on the nitrogen NMR shielding of N-nitrosamines and DFT     calculations of the nitrogen shieldings of C-nitroso, N-nitroso and O-nitroso systems, J.    Magn. Reson., 164, 212 (2003).

  5. E. Bednarek, J.Cz. Dobrowolski, K. Kamieńska-Trela, Theoretical and experimental 1H,    13C and 15N NMR spectra of monomethyl substituted tetramethyl 9aH- and 4H-quinolizine- 1,2,3,4-tetracarboxylate,  J. Mol. Struct., 651-653, 709-727 (2003).

  6. K. Ruszczyńska, K. Kamieńska-Trela, J. Wójcik, J. Stępiński, E. Darżynkiewicz, R.     Stolarski, Charge distribution in 7-methylguanine regarding cation-p interaction with       protein factor eIF4E, Biophysical Journal, 85, 1450 (2003).

  7. K. Kamieńska-Trela, L. Kania, M. Bechcicka, Ł. Kaczmarek , 13C NMR studies on the    structure of 5H- and 6H-indolo[2,3-b]quinolines and the related compounds, J. Mol. Struct.,   661-662C, 209 (2003).

  8.  E. Dvornikova, M.Bechcicka,  K. Kamieńska-Trela and A. Krówczyński, Synthesis and    NMR studies of 2- and 3-fluorosubstituted five-membered heterocycles, J. Fluorine Chem.,    124, 159 (2003).

  9.  Z. Biedrzycka and K. Kamieńska-Trela Influence of Substituents on Carbon-Carbon    Coupling Constants in Acetylenes, Pol. J. Chem., 77, 1637 (2003). 

  10. K. Kamieńska-Trela, P. Bernatowicz, W. Lüttke, R. Machinek, M. Trætteberg, One-bond 13C,13C coupling constants in alkyl-substituted cyclopropenes. Experimental and theoretical studies, Magn Reson.Chem. 40, 640 (2002). 

  11. E. Dvornikova, K. Kamieńska-Trela, Synthesis of 2- and 3-substituted N-methylpyrroles,  Synlett, 1152 (2002).

  1. M. Witanowski, Z. Biedrzycka, W. Sicińska, Z. Grabowski, A study of solvent polarity and hydrogen bonding effects on the nitrogen NMR shieldings of N-nitramines and ab initio calculations of the nitrogen shieldings of C-nitro, N-nitro and O-nitro systems, J. Mol. Struct., 602, 199 (2002).

  2. P. Cmoch, K. Kamieński, K. Kamieńska-Trela, L. Stefaniak, G. A. Webb, Furoxan rearrangement of some pyridofuroxan derivatives studied by 1H, 13C, 14N and 17O NMR spectroscopy, J. Phys. Org. Chem., 13, 480 (2000).
  3. M. Witanowski, Z. Biedrzycka, Z. Grabowski, Study of hydrogen bonding and solvent polarity effects on the nitrogen NMR shieldings of N, N-dimethylacetamide, Magn. Reson. Chem., 38, 177 (2000).
  4. A. Dąbrowski, K. Kamieńska-Trela, J. Wójcik, NMR studies on derivatives of heteroaromatic compounds; exceptionally small carbon-carbon couplings, 1J(CC), in 2-lithiothiophene, 2-lithio-N-methylpyrrole and 2-lithiofuran, Spectrochimica Acta A, 56, 91 (2000).
  5. M. Witanowski, Z. Biedrzycka, Z. Grabowski, Solvent effects on the nitrogen NMR shieldings of 3-methylsydnone and ab initio calculations of the shieldings including related oxazole and oxadiazole systems, Magn. Reson. Chem., 38, 580 (2000).
  6. K. Kamieńska-Trela, L. Kania, P. Bernatowicz, M. Bechcicka, Ł. Kaczmarek, J. Wójcik, Estimation of the total range of 1J(CC) couplings in heterocyclic compounds: pyridines and their oxides; the experimental and DFT studies. Spectrochimica Acta A, 56, 2079 (2000).
  7. M. Witanowski, Z. Biedrzycka, W. Sicińska, G. A. Webb, Nitrogen NMR shieldings of thiourea systems as a function of solvent polarity and hydrogen bond effects,          J. Mol. Struct., 516, 107 (2000).
  8. K. Kamieńska-Trela, L. Kania, W. Schilf, I. Balova, One-bond C-13-C-13 couplings in diacetylenes; experimental and theoretical studies, Spectrochimica Acta A, 55, 817 (1999).
  9. M. Witanowski, W. Sicińska, Z. Biedrzycka, G. A. Webb, Hydrogen Bond and Solvent Polarity Effects on the Nitrogen NMR Shielding of Urea Systems, J. Mol. Struct., 476, 133 (1999).
  10. M. Witanowski, Z. Biedrzycka, K. Grela, K. Wejroch, Nitrogen NMR Shieldings of Nitroalkanes as a Structural and Conformational Probe, Magn. Reson. Chem., 36, S85 (1998).
  11. M. Witanowski, Z. Biedrzycka, K. Grela, Nitro Group Effects on the 1JCC couplings in Nitroalkanes, Magn. Reson. Chem., 36, 356 (1998)
  12. B. G. Gowenlock, B. King, J. Pfab, M. Witanowski, Kinetic Studies of the Raction of some Nitrosoalkanes with Nitrogen Dioxide, J. Chem. Soc. Perkin 2, 483, (1998).
  13. M. Witanowski, Z. Biedrzycka, W. Sicińska, Z. Grabowski, A Study of Solvent Polarity and Hydrogen Bonding Effects on the Nitrogen NMR Shieldings of Isomeric Tetrazoles and Ab Initio Calculations of the Nitrogen Shieldings of Azole Systems,    J. Magn. Reson., 131, 54 (1998).
  14. M. Witanowski, Z. Biedrzycka, W. Sicińska, G. A. Webb, Solvent-induced Effects on the Nitrogen NMR Shieldings of Some Nitrosoarene Systems, Magn. Reson. Chem., 35, 262 (1997).
  15. M. Witanowski, W. Sicińska, Z. Biedrzycka, Z. Grabowski, G. A. Webb, Solvent and Protonation Effects on Nitrogen NMR Shieldings of Isoamides (a-Imino-ethers),          J. Mol. Struct., 404, 267 (1997).
  16. M. Witanowski, Z. Biedrzycka, W. Sicińska, G. A. Webb, Solvent-induced Variations in Nitrogen NMR Shieldings of Some Oxime Systems as a Test for the Solvaton Model of Non-specific Molecular Interactions, J. Chem. Soc. Perkin 2, 533 (1997).
  17. M. Witanowski, Z. Biedrzycka, W. Sicińska, Z. Grabowski, G. A. Webb, Hydrogen Bonding and Solvent Polarity Effects on the Nitrogen NMR Shielding of 1,2,4,5-Tetrazine, J. Magn. Reson. (A), 124, 127 (1997).
  18. M. Witanowski, W. Sicińska, Z. Biedrzycka, Z. Grabowski, G. A. Webb, Solvent Effects on the Nitrogen NMR Shieldings in Thiazole and Thiadiazole Systems, 
    J. Chem. Soc. Perkin 2, 619 (1996).
  19. M. Witanowski, Z. Biedrzycka, W. Sicińska, Z. Grabowski, G. A. Webb, Solvent Effects on the Nitrogen NMR Shieldings in Oxazole and Oxadiazole Systems, 
    J. Magn. Reson. (A), 120, 148 (1996).
  20. M. Witanowski, Z. Biedrzycka, G. A. Webb, Solvents Effects on the Nitrogen NMR Shielding of 2-Methyl-2-nitrosopropane and Its Azadioxy Dimer, Mag. Reson. Chem., 34, 233 (1996).
  21. M. Witanowski, W. Sicińska, Z. Biedrzycka, G. A. Webb, Solvent Effects on the Nitrogen NMR Shielding in Cyanamide and N,N-Dimethylcyanamide, J. Mol. Struct., 380, 133 (1996).