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First example of a high-level correlated calculation of the indirect spin-spin coupling constants involving tellurium: tellurophene and divinyl telluride

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  • Yury Yu Rusakov
  • Leonid B. Krivdin
  • Freja From Østerstrøm
  • Sauer, Stephan P. A.
  • Vladimir A. Potapov
  • Svetlana V. Amosova

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.

OriginalsprogEngelsk
TidsskriftPhysical Chemistry Chemical Physics
Vol/bind15
Udgave nummer31
Sider (fra-til)13101-13107
Antal sider7
ISSN1463-9076
DOI
StatusUdgivet - 2013

ID: 45880597