The constitution of a number of 2-(iminomethyl)benzenethiols and 2- (iminomethyl)-4-nitrobenzene-thiols has been studied by 1H N.M.R. spectroscopy. A zwitterionic imminium structure is suggested for all the compounds studied except for the 4'-methoxyphenylimine derivative which exists in the thiol form.

Carbon-based free radicals were generated by thermal cleavage of the tetraester Me2C(COOME)-CH2-CMe( COOMe )- CMe ( COOMe )-CH2-C( COOMe )Me2 which is a model for head-to-head units in a poly(methyl methacrylate ) chain. The resulting electron spin resonance spectrum had higher resolution than the 'nine-line' spectrum previously reported; this enabled identification of the component radicals. In the present case, the spectrum was well matched by a summation of spectra of the Me2C(COOME)-CH2-CMe( COOMe ) radical and the 1-methoxycarbonyl-1-methylethyl radical Me2-C-COOMe derived from it by loss of methyl methacrylate. Both of these radicals were generated in separate experiments. Radicals were also generated from starting materials containing a CD3 group in place of the single CH3.

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Calculations by the IPPP-INDO method give the spin-spin coupling constants for the side-chain carbons, 3JCF and 4JCF, as 4.97 and 6.86 Hz respectively with substantial contributions to through-space coupling from the pathway CO-C-H…F. The observed values for 1-(2- fluorophenyl ) ethanone , 3.3 and 7.2 Hz, and for 1-(2,5- difluorophenyl ) ethanone , 3.7 and 7.3 Hz, are in good agreement with these predictions. Two compounds, a dihydroindenone and a naphthalenone, in which this pathway cannot be effective, show no fluorine coupling to the aliphatic carbon next to the carbonyl and the values of 3JCF are reduced to 2.2 and 2.5 Hz, consistent with the loss of a through-space Fermi contact term of the kind described above.

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 π-type lone-pair does not contribute to the TS coupling pathway of the FC term.