Abstract
^13^C n.m.r. chemical shifts of a number of 1,1‐disubstituted ethylenes are presented. Moreover, effects of changing temperatures on the ^13^C n.m.r. chemical shifts of some of these compounds as well as of three normal alkanes are given. These variations in chemical shifts are attributed to varying amounts of sterically induced shifts in the different conformational equilibria. In addition to the well‐known 1,4 interaction between two alkyl groups shielding effects on the carbon atoms of the connecting bonds are also proposed. No definite explanation of this effect is presented at this time. It is further shown that no simple correlations exist between ^13^C n.m.r. chemical shifts and calculated total charge densities at this level. Instead, the experimental results in 1‐alkenes are rationalized by assuming a linear dependence of the ^13^C n.m.r. chemical shifts of C‐1 and C‐2 via rehybridizations on changes in bond angles for small skeletal deformations caused by steric interactions. These changes in geometries, as well as conformational energies in three 1‐alkenes, were calculated by means of VFF calculations. Finally. upfield shifts for both C‐2 and C‐4 are proposed for those conformations of 1‐alkenes in which the C‐3C‐4 group interacts with the p~z~‐orbital of C‐2.