The compds. Fe(CO)3(dRpf)n+, n=0, 1, 2 and dRpf=1,1'-bis(dicyclohexylphosphino)ferrocene (1n+) or 1,1'-bis(diisopropylphosphino)ferrocene (2n+), were obtained as two-step reversible redox systems by photolytic and redox reactions. The iron-iron distance decreases from about 4 \AA to about 3 \AA on oxidn., which takes place primarily at the tricarbonyliron moiety. Whereas ferrocene oxidn. is calcd. to occur only in excited states, the near IR absorptions of the mixed-valent monocations are due to an unprecedented \dqinverse\dq inter-valence charge transfer from the electron-rich iron(II) in the ferrocene backbone to the electron-deficient tricarbonyliron(I). Protonation of complex 1 results in the formation of the structurally characterized hydride 1HBF4, which reacts with acetone to form the dication, 12+, and isopropanol. While the hydride 2HBF4 was found to be unstable, protonation of 2 in acetone resulted in the clean formation of 22+, formally a hydrogen transfer. on SciFinder(R)
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