Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2009, Issue 21, Pages 3526-3534Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.200900197
Keywords
Relativistic effects; Density functional calculations; NMR spectroscopy; Tin
Categories
Funding
- University of Palermo [ORPA07SY2M]
- Fondazione Banco di Sicilia [PR 13.b/07]
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The empirical Karplus-type dependence of (3)J(Sn-119,C-13) and (3)J(Sn-119,H-1) couplings in organotin(IV) derivatives has been computationally validated by DFT methods both at the nonrelativistic and scalar ZORA relativistic level. A preliminary calibration of the computational protocols, by comparing experimental and calculated couplings for a Set Of Suitable rigid molecules, revealed their high predictive power: in particular, relativistic results for (3)J(Sn-119,C-13) have a mean absolute error of just above 2 Hz, over a range of values up to about 70 Hz. The latter protocol has then been used to study in detail the influence of substituents and multiple paths connecting the coupled nuclei on the vicinal coupling constants, Some conformational issues have been also considered. Significant effects have been observed and theoretical Karplus-type curves for some representative systems have been proposed and discussed. It appears that general equations for vicinal Sn-119-H-1 and Sn-119-C-13 couplings cannot be derived, although the shape of the curves is preserved with vertical bar(3)J(0 degrees)vertical bar < vertical bar(3)J(180 degrees)vertical bar and (3)J(90 degrees)vertical bar approximate to 0 Hz. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
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