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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Stereochemical dependence of NMR geminal spin-spin coupling constants

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Author(s):
Contreras, Ruben H. [1] ; Provasi, Patricio F. [2, 3, 4] ; dos Santos, Francisco P. [5] ; Tormena, Claudio F. [5]
Total Authors: 4
Affiliation:
[1] Univ Buenos Aires, FCEyN, Dept Phys, Buenos Aires, DF - Argentina
[2] Consejo Nacl Invest Cient & Tecn, RA-1033 Buenos Aires, DF - Argentina
[3] Northeastern Univ, FACENA, Dept Phys, Corrientes - Argentina
[4] Consejo Nacl Invest Cient & Tecn, Corrientes - Argentina
[5] Univ Estadual Campinas, Dept Organ Chem, Inst Chem, BR-13084971 Sao Paulo - Brazil
Total Affiliations: 5
Document type: Journal article
Source: Magnetic Resonance in Chemistry; v. 47, n. 2, p. 113-120, FEB 2009.
Web of Science Citations: 13
Abstract

In this work it was sought to explore the versatility of germinal spin-spin coupling constants, (2)J(XY) SSCCs, as probes for stereochemical studies. A set of compounds, where their experimental (2)J(XY) SSCCs through the X-C-Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom ('coupling pathway'), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule I(M) - hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to (2)K(XY) reduced spin-spin coupling constants (RSSCC), and Rule II(M) - hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to (2)K(XY) RSSCC. Copyright (C) 2008 John Wiley \& Sons, Ltd. (AU)

FAPESP's process: 05/59649-0 - Conformational equilibria studies by nuclear magnetic resonance spectroscopy, infrared spectroscopy and theoretical calculations
Grantee:Roberto Rittner Neto
Support Opportunities: Research Projects - Thematic Grants