Steric and Electronic Interactions Between Cofacial Metallocene Rings
Regina Arnold, Bruce M. Foxman, Myron Rosenblum, William B. Euler, Organometallics, 1988, 7, 1253 1259
As part of a study of interactions between metallocenes, held so that two cyclopentadienyl rings are constrained to be proximate and facing one another, 1,8-diruthenocenylnaphthalene (1b) has been prepared and its crystal structure has been determined. This structure is shown to be close to that of 1,8-diferrocenylnaphthalene (1a) reported earlier, especially in respect to the dihedral angle between the substituted cyclopentadienyl and naphthalene ring planes and the splay angle between the two substituted cyclopentadienyl rings. Both of these distortions are significantly diminished in the monocation derived from 1a, suggesting that there is a significant decrease in electron density on the cyclopentadienyl rings on oxidation of ferrocene to ferricenium cation, consistent with theoretical analyses.