Radula-Janik, Klaudia2; Kupka, Teobald2; Ejsmont, Krzysztof2; Daszkiewicz, Zdzislaw2; Sauer, Stephan P. A.3
1 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet2 Opole University3 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet
Structures of selected 3,6-dihalogeno-N-alkyl carbazole derivatives were calculated at the B3LYP/6-311++G(3df,2pd) level of theory and their 13C NMR isotropic nuclear shieldings were predicted using density functional theory (DFT). The model compounds contained 9H-, N-methyl and N-ethyl derivatives. The relativistic effect of Br and I atoms on nuclear shieldings was modeled using the spin-orbit ZORA method. Significant heavy atom shielding effects for the carbon atom directly bonded with bromine and iodine were observed (~ -10 and ~ -30 ppm while the other carbon shifts were practically unaffected). The decreasing electronegativity of the halogen substituent (F, Cl, Br and I) was reflected in both nonrelativistic and relativistic NMR results as decreased values of chemical shifts of carbon atoms attached to halogen (C3 and C6) leading to a strong sensitivity to halogen atom type at 3 and 6 positions of the carbazole ring. The predicted NMR data correctly reproduce the available experimental data for unsubstituted N-alkylcarbazoles.
Magnetic Resonance in Chemistry, 2013, Vol 51, Issue 10, p. 630-635
The Faculty of Science; NMR; carbazole; chemical shift; relativistic effects; quantum chemistry; computational chemistry; density functional theory; DFT