
%0 Journal Article
%A Rae, ID 
%A Rae, ID 
%A Staffa, A 
%A Staffa, A 
%A Diz, AC 
%A Diz, AC 
%A Giribet, CG 
%A Giribet, CG 
%A Deazua, MCR 
%A Deazua, MCR 
%A Contreras, RH 
%A Contreras, RH 
%T Through-Space Transmission of <sup>19</sup>F-<sup>13</sup>C Coupling Via an Intermediate Bond. An Experimental and Theoretical Study
%J Australian Journal of Chemistry
%D 1987/12/01
%V 40
%N 12
%P 1923-1940
%K 
%R https://doi.org/10.1071/CH9871923
%U https://www.publish.csiro.au/paper/CH9871923 
%X In order to obtain a deeper insight into the title effect, several compounds with an F atom very close to a C-H of a nearby functional group were synthesized and the relevant couplings measured. The most conspicuous case was that of 8-fluoro-2-hydroxynaphthalene-1-carbaldehyde where a close proximity between the F and H atoms is the result of fluorine-oxygen repulsion and the formation of an intramolecular hydrogen bond between the hydroxyl and carbonyl groups. The experimental four-bond J(F,CHO) coupling is 26.2 Hz. A compound very similar to this one, but without the OH group, was chosen on which to perform a polarization propagator analysis of the through-space (TS) coupling pathways, at the RPA-INDO level. The expression for the TS coupling in terms of the projected polarization propagator and perturbators was numerically analysed. It is found that this coupling is completely dominated by a TS component of the Fermi contact (FC) term, the main features of which are: ( i ) It decays exponentially with the F-H distance; (ii) Its main contribution comes from an electron excitation involving the F lone-pair, the C-H bond of the CHO moiety and its corresponding antibonding orbital;(iii) The &#960;-type lone-pair does not contribute to the TS coupling pathway of the FC term. 
