| Full text | |
| Author(s): |
Anizelli, Pedro R.
[1]
;
Favaro, Denize C.
[1]
;
Contreras, Ruben H.
[2, 3]
;
Tormena, Claudio F.
[1]
Total Authors: 4
|
| Affiliation: | [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 |
| Abstract | |
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 |