Interpretation of the Longitudinal 13C Nuclear Spin Relaxation and Chemical Shift Data for Five Bromoazaheterocycles Supported by Nonrelativistic and Relativistic DFT Calculations

Autor: Anna Kraska-Dziadecka, Adam Gryff-Keller, Dominika Kubica, Artur Wodyński
Rok vydání: 2015
Předmět:
Zdroj: The Journal of Physical Chemistry A. 119:517-524
ISSN: 1520-5215
1089-5639
DOI: 10.1021/jp510687x
Popis: The longitudinal relaxation times of (13)C nuclei and NOE enhancement factors for 2-bromopyridine (1), 6-bromo-9-methylpurine (2), 3,5-dibromopyridine (3), 2,4-dibromopyrimidine (4), and 2,4,6-tribromopyrimidine (5) have been measured at 25 °C and B0 = 11.7 T. The most important contributions to the overall relaxation rates of nonbrominated carbons, i.e., the relaxation rates due to the (13)C-(1)H dipolar interactions and the shielding anisotropy mechanism, have been separated out. For 3 and 5, additionally, the T2,Q((14)N) values have been established from (14)N NMR line widths. All of these data have been used to determine rotational diffusion tensors for the investigated molecules. The measured saturation recovery curves of brominated carbons have been decomposed into two components to yield relaxation times, which after proper corrections provided parameters characterizing the scalar relaxation of the second kind for (13)C nuclei of (79)Br- and (81)Br-bonded carbons. These parameters and theoretically calculated quadrupole coupling constants for bromine nuclei have allowed the values of one-bond (13)C-(79)Br spin-spin coupling constants to be calculated. Independently, the coupling constants and magnetic shielding constants of the carbon nuclei have been calculated theoretically using the nonrelativistic and relativistic DFT methods F/6-311++G(2d,p)/PCM and so-ZORA/F/TZ2P/COSMO (F = BHandH or B3LYP), respectively. The agreement between the experimental and theoretical values of these parameters is remarkably dependent on the theoretical method used.
Databáze: OpenAIRE
Externí odkaz: