Diels−Alder Reactions of 3-Ferrocenyl-2,4,5-triphenylcyclopentadienone:  Syntheses and Structures of the Sterically Crowded Systems C₆Ph₅Fc, C₇Ph₆FcH, and [C₇Ph₆FcH][SbCl₆]

Abstract

Diels−Alder addition of diphenylacetylene or of 1,2,3-triphenylcyclopropene to 3-ferrocenyl-2,4,5-triphenylcyclopentadienone yields, upon thermolysis, C 6 Ph 5 Fc ( 5 ) or C 7 Ph 6 FcH ( 8 ), respectively. Subsequent treatment of 8 with triethyloxonium hexachloroantimonate results in the formation of the ferricinium complex [C 7 Ph 6 FcH] + [SbCl 6 ] - ( 13 ), rather than the anticipated tropylium cation [C 7 Ph 6 Fc] + . The substituted ferrocene derivatives 5, 8, and 13 have been characterized by X-ray crystallography. From the solid-state structure of 5 it is evident that the peripheral aryl substituents do not adopt a regular propeller type conformation, but instead exhibit an incremental progression of twist angles relative to the central ring. The dynamics of peripheral ring rotations in 5 and 8 have been studied by variable-temperature NMR.