GROUP-IV DOUBLE-BONDS - SHAPE DEFORMATION AND SUBSTITUENT EFFECTS

A unified explanation of deformation and substituent effects is given for group IV double bonds. Results from experiments and previous theoretical work are correlated with ab initio calculations on electron withdrawal by substituents to determine the factors that govern geometry and bonding. Predictions are made and calculations carried out for a silyl substituent as a test of our hypotheses. In order to systematically investigate substituent effects we have adopted a nuclear charge perturbation approach. The GAUSSIAN set of ab initio electronic structure programs has been modified so that a continuous range of electron withdrawal is available. © 1990, American Chemical Society. All rights reserved.