This paper documents a very first example of a high-level correlated calculation of spin-spin coupling constants involving tellurium taking into account relativistic effects, vibrational corrections and solvent effects for the medium sized organotellurium molecules. The 125Te-1H spin-spin coupling constants of tellurophene and divinyl telluride were calculated at the SOPPA and DFT levels in a good agreement with experiment. A new full-electron basis set av3z-J for tellurium derived from the "relativistic" Dyall's basis set, dyall.av3z, and specifically optimized for the correlated calculations of spin-spin coupling constants involving tellurium, was developed. The SOPPA methods show much better performance as compared to 15 those of DFT, if relativistic effects calculated within the ZORA scheme are taken into account. Vibrational and solvent corrections are next to negligible, while conformational averaging is of prime importance in the calculation of 125Te-1H spin-spin couplings. Based on the performed calculations at the SOPPA(CCSD) level, a marked stereospecificity of geminal and vicinal 125Te-1H spin-spin coupling constants originated in the orientational lone pair effect of tellurium has been established which opens a 20 new guideline in the organotellurium stereochemistry.
Physical Chemistry Chemical Physics, 2013, Vol 15, Issue 31, p. 13101-13107
NMR Spectroscopy; Spin-spin coupling constant; relativistic effects; ab initio HF and DFT computations; Computational Chemistry; Quantum Chemistry; tellurium; The Faculty of Science