Computational protocols for the 19F NMR parameters. Part 2: Fluorobenzenes

•The calculations of fluorine-fluorine, fluorine-carbon, and fluorine-proton spin-spin coupling constants (165 couplings in total) are performed for all possible fluorobenzenes ranging from fluorobenzene to hexafluorobenzene within different computational approaches based on the SOPPA, CCSD and DFT formalisms with taking into account solvent, vibrational, and correlation corrections. A good correlation of calculated couplings at all levels with experiment was established.•Solvent corrections are in average of about 0.2‒0.3 Hz in absolute value for the long-range (geminal, vicinal, and longer range) couplings involving fluorine, while they are essentially larger (up to several Hertz) for the one-bond carbon-fluorine couplings.•Vibrational corrections are even smaller, being in average of about 0.1‒0.2 Hz and alternating in sign, while they are negative and somewhat larger in absolute value (up to ‒3.9 Hz) for the one-bond carbon-fluorine couplings.•Electron correlation corrections are much more pronounced for the fluorine-fluorine and one-bond fluorine-carbon spin-spin coupling constants, reaching up to 7 and 11 Hz for these types of couplings, respectively. However, these are crucial only for the correct calculation of fluorine-fluorine couplings and are rather less important for the fluorine-carbon couplings, because the ranges of these couplings are cardinally different, being of −1.6 ± 19.2 Hz for the former and -240 ± 10 Hz for the latter. All possible fluorine spin-spin coupling constants, 19F‒19F, 19F‒13C, and 19F‒1H, in the series of 12 fluorobenzenes, ranging from fluorobenzene to hexafluorobenzene, were calculated using three different non-empirical formalisms, those based on the DFT, SOPPA, and CCSD formalisms with taking into account solvent, vibrational, and correlation corrections. Within the DFT formalism, three exchange-correlation functionals, namely KT3, M06–2X, and PBE0, were found to be most suitable for the calculation of 19F‒19F, 19F‒13C, and 19F‒1H couplings. Among computational schemes based on the SOPPA and CCSD formalisms, the most efficient and accurate scheme for the calculation of 19F‒13C and 19F‒1H SSCCs is the SOPPA(MP2), while that for the 19F‒19F coupling constants, it is the composite scheme SOPPA(MP2)/CCSD. [Display omitted]