Crystallographic characterization of the geometry changes upon electron loss from 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octanes

Abstract

Crystal structures of 2-tert-butyl-3-(2,3,5,6-tetramethylphenyl)-2,3- diazabicyclo[2.2.2]-octane radical cation nitrate (HyDU+NO 3-) [Hy = (2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl]; 2-tert-butyl-3-(1-naphthyl)-2,3-diazabicyclo[2.2.2]octane radical cation hexafluoroantiminate (Hy1NA+SbF6-); 2-tert-butyl-3-(2-naphthyl)-2,3-diazabicyclo-[2.2.2]octane radical cation hexafluoroantiminate (Hy2NA+SbF6-); 1,5-bis(2-tert-butyl-2,3-diazabicyclo-[2.2.2]oct-3-yl)naphthalene dication bis(tetraphenylborate) (Hy215NA2+(Ph 4B-)2); and 2,7-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)naphthalene dication bis(hexafluoroantiminate) (Hy227NA2+(SbF6-) 2·CH3CN) are reported, and the geometries about the oxidized Hy units compared with literature data for neutral Hy-substituted analogues and the geometry changes upon electron loss for these compounds, which have a lone pair, lone pair twist angle in the neutral form (θ(0)) in the range 122-130°, are compared with those for tetraalkylhydrazines that have θ(0) values near 180, 90, and 0°. © 2005 American Chemical Society.