Vicinal 1H, 13C coupling constants were measured for rigid unsaturated 1H-C-C=13C molecular frameworks at natural abundance. As a general trend, an empirical range of 4.5-6.5 Hz is observed independent of the value of the dihedral angle between the CH bond and the plane of the double bond. Furthermore, through-bond and through-space substituent effects also influence the magnitude of the coupling constants in a similar way to that known for saturated systems. In summary, two different additive transmission mechanisms take part in these coupling paths depending on the orientation of the π-system with respect to the allylic bond. The experimental evidence presented demonstrates the breakdown of the Karplus rule in this particular structural fragment.
|Journal||Magnetic Resonance in Chemistry|
|Publication status||Published - 1 Jan 1997|
- 1 H NMR
- Allylic systems
- Long-range proton-carbon coupling constants
Parella, T., Sánchez-Ferrando, F., & Virgili, A. (1997). Experimental evidence for the breakdown of the karplus relationship for 3J(13C, 1H) in 1H-C-C=13C systems. Magnetic Resonance in Chemistry, 35(1), 30-34. https://doi.org/10.1002/(SICI)1097-458X(199701)35:1<30::AID-OMR21>3.0.CO;2-0