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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.)

Effect of Electronic Interactions on NMR (1)J(CF) and (2)J(CF) Couplings in cis- and trans-4-t-Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives

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Anizelli, Pedro R. [1] ; Favaro, Denize C. [1] ; Contreras, Ruben H. [2, 3] ; Tormena, Claudio F. [1]
Total Authors: 4
[1] Univ Estadual Campinas, Inst Chem, BR-13084971 Campinas, SP - Brazil
[2] Consejo Nacl Invest Cient & Tecn, IFIBA, RA-1033 Buenos Aires, DF - Argentina
[3] Univ Buenos Aires, FCEyN, Dept Phys, Buenos Aires, DF - Argentina
Total Affiliations: 3
Document type: Journal article
Source: Journal of Physical Chemistry A; v. 115, n. 22, p. 5684-5692, JUN 9 2011.
Web of Science Citations: 19

In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on (1)J(CF) and (2)J(CF) NMR spin-spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of (2)J(CF) SSCC in cis- 4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds. (AU)

FAPESP's process: 08/06282-0 - Transmission mechanism of scalar spin-spin coupling constants involving fluorine atom.
Grantee:Roberto Rittner Neto
Support type: Regular Research Grants
FAPESP's process: 10/10993-9 - Transmission mechanism through space scalar coupling constants in NMR
Grantee:Claudio Francisco Tormena
Support type: Regular Research Grants