The synthesis and properties of molecules in which two relatively unreactive functional groups are forced into close proximity to each other will be studied. Particular emphasis will be placed on in-cyclophanes bearing phosphine lone-pair electrons brought into close proximity with aromatic rings. Other electron-rich groups, such as olefins, amines, phosphine oxides, and silyl fluorides will also be examined. By balancing the forces due to intramolecular strain in these compounds with the nucleophilicity or electrophilicity of the aromatic ring, it may be possible to obtain structures in which there is partial bonding between the groups in question. Such structures may serve as models for transition state structures in ordinary aromatic reactions. A second part of the project will involve the synthesis and study of the physical properties of fullerene fragments. Each of these fragments will be a different segment of buckminsterfullerene (spherical C60). %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Robert Pascal at Princeton University. the main focus of the project is the synthesis and study of highly strained organic molecules, i.e., molecules in which some atoms are forced by steric constraints to occupy positions which lead to unnatural interactions with other atoms and to unusual bond distances and angles. Of particular interest are the structure and reactivity of molecules in which two relatively unreactive functional groups are forced to be very close together. It is expected that the enforced proximity will lead to unusual reactivity for the groups involved,and to unusual physical properties as well. In another part of this project, fragments of a recently discovered spherical C60 allotrope of carbon (other allotropes of carbon are diamond and graphite) will be prepared in order to understand how C60 may be formed from carbon fragments.
