Over 100 isotope effects on C-13 chemical shifts were determined in a
series of deuteriated cis-stilbene isotopomers. The magnitude and sign
of these effects depend on the position and the number of deuterium a
toms in the molecule, The variations in two- and three-bond effects we
re rationalized by steric interactions between the phenyl ring and the
olefinic group, The six-bond effects in cis-stilbene isotopomers are
related to the molecular Ph-C= C dihedral angle, as in other binuclear
aromatic molecules, In [para-H-2]-cis-stilbene the isotope effect ove
r ten bonds was observed, amounting to 2.0 ppb. In mono- and dideuteri
o-cis-stilbenes, effects over up to three bonds from the site of the d
euteriation have a positive sign and decrease monotonously in magnitud
e, In contrast, effects through more than three bonds generally show a
n alternation in sign and oscillations in magnitude, In polydeuteriate
d cis-stilbenes, changes in sign and magnitude are governed by the add
itivity rule, which reproduces the observed values of isotope effects
within a few percent.