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Computational Chemistry at the Department of Synthesis

Contact: Drahomír Hnyk

Computational chemistry as well as structural chemistry of borane, heteroborane and metallaborane cluster are pursued on a few fronts. The most important target are theoretical computations of different variables, in this respect examination of molecular geometries and shielding tensors prevail. 11B NMR spectroscopy is the method of choice for establishing architectures of these kinds of materials. The computed 11B NMR chemical shifts are confronted with experimental values and the level of agreement between the experimental and computed values reveal the measure of correctness of the molecular geometries in solutions. The reaction pathways are also computationally searched, basically in terms of examing the corresponding transition states and intermediates on going from already known or still unkown starting materials toward the products.

Due to a very productive liaison with the Institute of Organic Chemistry and Biochemistry of the CAS, various interactions of boranes with biomolecules are being investigated. The same applies to noncovalent interactions in crystals, in which hydrogen bonds, dihydrogen bonds and interactions of the so-called σ-holes (they are responsible for creating halogen, chalkogen, and pnictogen bonds)  represent driving forces during the crystallization procedures. The computational studies of heats of formation of boron clusters in relation to experimental values are also carried out.

 

References

  1. Baše, T., Holub, J., Fanfrlík, J., Hnyk, D., Lane, P. D., Wann, D. A., Vishnevskiy, V., Tikhonov, D., Reuter, Ch. and Mitzel, N. W.: ICOSAHEDRAL CARBABORANES WITH PERIPHERAL HYDROGEN-CHALCOGENIDE FUNCTIONS: THEIR STRUCTURES FROM GAS ELECTRON DIFFRACTION AND CHEMICAL SHIELDING IN SOLUTION, Eur. J., 2019, 25, 2313 – 2321.
  2. Frances-Monerris, A., Holub, J.; Roca-Sanjuán, D., Hnyk, D., Lang, K. and Oliva-Enrich, J. M.: PHOTOCHROMIC SYSTÉM AMONG BORON HYDRIDES: THE HAWTHORNE REARRANGEMENT, Phys. Chem. Lett., 2019, 10, 6202 – 6207.
  3. Holub, J., Vrána, J., Růžička, A., Růžičková, Z., Fanfrlík, J. and Hnyk, D.: THIABORANES ON BOTH SIDES OF THE ICOSAHEDRAL BARRIER: RETAINING AND BREAKING THE BARRIER WITH CARBON FUNCTIONALITIES, ChemPlusChem, 2019, 84, 822 – 827.
  4. Holub, J.; Vishnevskiy, Y.V.; Fanfrlík, J.; Mitzel, N.W.; Tikhonov, D.: Schwabedissen, J.; McKee, M.L.; Hnyk, D.: BROMINATION MECHANISM OF CLOSO-1,2-C2B10H12 AND THE STRUCTURE OF THE RESULTING 9-Br-CLOSO-1,2-C2B10H11 BY GAS ELECTRON DIFFRACTION, ChemPlusChem, 2020, 85, 2606-2610.
  5. Bakardjiev, M.; Holub, J.; Růžičková, Z.; Fanfrlík, J.; Štíbr, B.; McKee, M. L. and Hnyk, D.: TRANSFORMATION OF VARIOUS MULTICENTER BONDINGS WITHIN BICAPPED-SQUARE ANTIPRISMATIC MOTIFS: Z-REARRANGEMENT, Dalton Trans. 2021, 50, 12019 – 12334.
  6. Vrána, J.; Holub, J.; Samsonov, M. A.; Růžičková, Z.; Cvačka, J.; McKee, M. L.; Fanfrlík, J.; Hnyk, D. and Růžička, A.: ACCESS TO CATIONIC POLYHEDRAL CARBORANES VIA DYNAMIC CAGE SURGERY WITH N-HETEROCYCLIC CARBENES, Commun. 2021, 12, 4971.
  7. Fanfrlík, J.; Brynda, J.; Kugler, M.; Lepšík, M.; Pospíšilová, K.; Holub, J.; Hnyk, D.; Nekvinda, J.; Grüner, B. and Řezáčová, P.: B-H..π AND C-H..π INTERACTIONS IN PROTEIN-LIGAND COMPLEXES: CARBONIC ANHYDRASE II INHIBITION BY CARBORANE SULFONAMIDES, Chem. Chem. Phys., 2023, 25, 1728.
  8. Keller, W.; Ballmann, J..; Sárosi, M.B.; Fanfrlík, J. and Hnyk, D.: THE TELLURABORANES CLOSO-TeB5Cl5 and CLOSO-TeB11Cl11 WITH EXCEPTIONALLY LONG BODY DIAGONALS: SYNTHETIC AND BONDING MOTIFS FOR INNOVATIVE OCTAHEDRAL AND ICOSAHEDRAL GEOMETRIES, Chem. Int. Ed., 2023, 62, e202219018.
  9. Keller, W.; Sárosi, M.B.; Fanfrlík, J.; Straka, M.; Holub, J.; McKee, M. L. and Hnyk, D.: BORON-BASED OCTAHEDRAL DICATION EXPERIMENTALLY DETECTED: DFT SURFACE CONFIRMS ITS AVAILABILITY, RSC Adv. 2023, 13, 19627.