Secondary Deuterium Isotope Effects in Solvolyses of Small-ring Compounds.

M.I.T. Quart. Prog. Rept., 50, 11 (1963); (f) McLean, A. D., J. Chem. Phys., 32, 1959 (1960). 6 Clementi, E., C. Roothaan, and M. Yoshimine, Phys. Rev., 127, 1618 (1962). 7K = 1.75, a(2s)= -0.559 au; a(2p)= -0.312 au; a(H) -0.50 au. 8 For BH a(2s) = -0.909 au; a(2p) = -0.314 au; a(H) = -0.591 au. For BB a(2s) -0.920 au; a(2pr) = -0.189 au; a(2pir) = -0.179 au. 9 Newton, M. D., unpublished work. In all diatomics studied (CO, C2, B2) K7r was quite large. In C2 38 (internuclear distance that of ethane) Keg was 6.35, whereas in staggered ethane [Pitzer, R. M., and W. N. Lipscomb, J. Chem. Phys., 39, 1995 (1963)] the same pair of orbitals (which can now interact with E' and E' symmetry orbitals formed from the hydrogens) had a relatively normal Kay of 2.31. It is tempting to speculate that in larger molecules where full valency is used, the Kay anomaly will disappear.