DFT studies of the conformational/structural dependencies of geminal 1H,1H scalar coupling 2J(H,H') in substituted...

A study is presented of the structural dependencies for scalar, interproton J-coupling across two bonds in a series of substituted methanes. The coupled perturbed, density functional theory method with a B3PW91 functional and aug-cc-pVTZ-J basis sets is used to examine coupling between geminal protons (2)J(H,H') in methane and a series of substituted compounds CH(3)X (X = CH3, CH(2)CH(3), CH=CH2, CH=O, and NH2) as functions of the dihedral angle phi measured about the C1-X2 bonds. All four contributions are obtained but all conformational effects are dominated by the Fermi contact term. Simple linear combination of atomic orbitals (LCAO)-molecular orbital (MO) sum-over-states methods are used to examine the relationships of the coupling constants with dihedral angles as well as internal H-C-H and H-C1-X2 angles. This study explores some novel aspects of geminal H-H coupling including an analysis of the asymmetry in the conformational dependencies arising from non-next-nearest neighbor interactions. For each of the substituted methanes, explicit trigonometric/exponential expressions are given and these accurately reproduce the (2)J(H,H') structural dependencies with standard deviations usually less than 0.03 Hz. The molecular structures for representative bicyclic molecules were fully optimized, and DFT results for (2)J(H,H') reproduce all the trends in the experimental data. A discussion is given on the applicability of the equations for H--H coupling in the substituted methanes to coupling in the bicyclic molecules.