Experimental and DFT studies on the transmission mechanisms of analogous NMR JCH and JCC couplings in 1-X- and 1-X-3-methylbicyclo[1.1.1]-pentanes.

The main aim of this work is to compare the transmission mechanisms for the Fermi contact term of spin-spin couplings, SSCCs, in series 1-X-bicyclo[1.1.1]-pentane, (1), and 1-X-3-methylbicyclo[1.1.1]pentane, (2), and from that comparison to gain insight into some subtle aspects of the FC transmission. To this end, 18 members of the latter series were isotopically enriched in (13)C at the methyl position and the following couplings were measured; 1JC3CMe, 3JC1CMe and 4JCXCMe. These three types of SSCCs in (2) are compared, respectively, with 1JC3H3, 3JC1H3 and 4JCXH in (1); these latter values were taken from previous works. Since electron delocalization plays an important role in the transmission of the FC interaction, the natural bond orbital (NBO) method is employed to quantify electron delocalization interactions within selected members of series (1) and (2). It is found that 1JC3H3 SSCCs in (1) is more efficiently transmitted than 1JC3CMe SSCCs in (2). On the other hand, 3JC1H3 and 4JCXH SSCCs in (1) are notably less efficiently transmitted than 3JC1CMe and 4JCXCMe SSCCs in (2), although substituent effects on these two SSCCs show the opposite trends. These different efficiencies are rationalized in terms of different sigma-hyperconjugative interactions in both series of compounds.

Experimental and theoretical study of hyperconjugative interaction effects on NMR 1J(CH) scalar couplings.

Hyperconjugative and electrostatic interactions effects on 1J(CH) spin-spin coupling constants (SSCCs) are critically studied from both theoretical and experimental points of view. A qualitative model is used to predict how the former affect such SSCCs, while electrostatic interactions are modeled with a point charge placed in the vicinity of the corresponding sigma(CH) bond. Hyperconjugative interactions are calculated using the "natural bond orbital" approach, and using the point-charge model, it is shown how intertwined are both types of interactions. Several members of the series 1-X-bicyclo[1.1.1]pentane and 1-X-3-methylbicyclo[1.1.1]pentane are chosen as model compounds for measuring 1J(CH) SSCCs; in some of them were performed also DFT-SSCC calculations. The strained cage substrate in these series defines strong sigma-hyperconjugative interactions, making these compounds excellent examples to verify the qualitative model presented in this work. It is verified that (a) hyperconjugative interactions from the sigma(CH) bond or into the sigma(CH) antibond containing the coupling nuclei yield a decrease of the corresponding 1J(CH) SSCC and (b) hyperconjugative interactions from other bonds involving the coupling C nucleus yield an increase of that 1J(CH) SSCC.

Influence of sigma-hyperconjugative interactions on 13C substituent chemical shifts: experimental and theoretical study in 1-X,3-CH3-bicyclo[1.1.1]pentanes.

(13)C chemical shifts were measured for 18 1-X,3-CH(3)-bicyclo[1.1.1]pentanes and the corresponding (13)C substituent chemical shifts (SCSs) were compared with those measured previously for the corresponding 1-X-bicyclo[1.1.1]pentanes. DFT-B3LYP calculations of GIAO magnetic shielding constants and of natural bond orbitals were carried out in order to gain an insight into factors defining the observed differences in (13)C SCSs in both series. These differences are rationalized in terms of substituent effects on sigma-hyperconjugative interactions.

Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study.

One- two- and three 13C, 13C (n = 1, 2, 3) scalar couplings, (n)J(C,C) in a set of pyrimidine derivatives were studied both experimentally at natural abundance and theoretically by their DFT calculation of all four contributions. Trends of non-contact terms are discussed and substituent effects are rationalized, comparing some of them with the corresponding values in benzene and pyridine. Although substituent effects on non-contact terms are relatively important, the whole trend is dominated by the Fermi contact term. According to the current literature, substituent effects on 1J(C,C) couplings in benzene derivatives are dominated by the inductive effect, which, apparently, is also the case in nitrogen heteroaromatic compounds. However, some differences observed in this work for substituent effects on 1J(C,C) couplings in pyrimidine derivatives suggest that in the latter type of compounds substituent effects can be affected by the orientation of the ring nitrogen lone pairs.