The Perlin Effect: bond lengths, bond strengths, and the origins of stereoelectronic effects upon one-bond C–H coupling constants

The magnitude of a one-bond C–H coupling constant depends upon the chemical environment of the hydrogen atom and, especially, upon its stereochemical relationship to vicinal lone electron pairs. However, a lone electron pair is not essential for the observation of a stereoelectronic effect, since even cyclohexane exhibits different axial and equatorial C–H coupling constants. We propose the name "Perlin Effect" to describe such observations. An analysis of the extensive experimental data regarding the Perlin Effect reveals that, in cyclohexane and in six-membered rings having one or more heteroatoms of the first row attached to the carbon of interest, 1JC–H is always larger for an equatorial hydrogen than for an axial hydrogen. The magnitude of the Perlin Effect is reduced when the carbon carrying the hydrogen of interest is attached to first row and second row atoms or heteroatoms, and it reverses when the carbon atom carries two heteroatoms from below the first row.The existence of the Perlin Effect in ...