Sterically Crowded Bicyclo[1.1.0]butane Radical Cations

The variability of carbon−carbon single bonds by steric and electronic effects is probed by DFT calculations of sterically crowded bicyclo[1.1.0]butanes and their radical cations. The interplay of sterics and electronics on the gradual weakening and breaking of bonds was studied by investigating bridgehead substitution in 1,3-di-tert-butylbicyclo[1.1.0]butane and 2,2‘,4,4‘-tetramethyl-1,3-di-tert-butylbicyclo[1.1.0]butane and geminal substitution in 2,2‘-di-tert-butylbicyclo[1.1.0]butane and 2,2‘,4,4‘-tetra-tert-butylbicyclo[1.1.0]butane. Bridgehead substitution leads to a lengthening of the central bond, whereas bisubstitution on the geminal carbon leads to a shortening of this bond due to a Thorpe−Ingold effect. Although the character of the central bond can be modulated by substitution and electron transfer over a range of 0.35 Å, the state forbidden ring planarization does not occur. Sterically crowded bicyclo[1.1.0]butane radical cations are therefore promising candidates for the investigation of extremely long carbon−carbon single bonds.