TY - JOUR
T1 - First example of a high-level correlated calculation of the indirect spin-spin coupling constants involving tellurium
T2 - tellurophene and divinyl telluride
AU - Rusakov, Yury Yu
AU - Krivdin, Leonid B.
AU - Østerstrøm, Freja From
AU - Sauer, Stephan P. A.
AU - Potapov, Vladimir A.
AU - Amosova, Svetlana V.
PY - 2013/8/21
Y1 - 2013/8/21
N2 - This paper documents the 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 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 good agreement with experimental data. 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 method shows a much better performance compared to 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 originating in the orientational lone pair effect of tellurium has been established, which opens a new guideline in organotellurium stereochemistry.
AB - This paper documents the 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 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 good agreement with experimental data. 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 method shows a much better performance compared to 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 originating in the orientational lone pair effect of tellurium has been established, which opens a new guideline in organotellurium stereochemistry.
KW - Faculty of Science
KW - NMR Spectroscopy
KW - Spin-spin coupling constant
KW - relativistic effects
KW - ab initio HF and DFT computations
KW - Computational Chemistry
KW - Quantum Chemistry
KW - tellurium
U2 - 10.1039/c3cp51462e
DO - 10.1039/c3cp51462e
M3 - Journal article
C2 - 23824065
SN - 1463-9076
VL - 15
SP - 13101
EP - 13107
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 31
ER -