On the planarity of tetracoordinate carbon enclosed by annulene perimeters

Abstract

Proposals that planar tetracoordinate carbon might be achieved by enclosure in an annulene perimeter have been examined by means of MNDO calculations. Unfortunately, the lowest energy forms of 1-3, and 5 are indicated to distort as far away from planarity as possible, consistent with the strain demands of the carbon skeletons. Even in hypothetical stereomutation transition states, planar tetracoordination around the central carbon should be energetically difficult to achieve in these hydrocarbons, which, at best, are expected to be unstable strained polyolefins. Planar tetracoordinate carbon is more likely to be achieved when both p and s systems provide effective stabilization through multicenter bonding. Several illustrative proposals for experimental examination are presented.