Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles.

The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η-CH)(η-CH); R = H, ; Bu, ; CHCH(OCHCH)OMe, ), [M(κ,'-FcC(O)CHC(O)Fc)] (M = Ti, = 3, ; M = Fe, = 3, ; M = BF, = 1, ), and 1-R'-3,5-Fc-CHN (R' = H, ; Me, ; Ph, ) is discussed. The solid-state structures of , , , , , , and ([TiCl(κ,'-PhC(O)CHC(O)Ph)]) show that and exist in their β-diketo form. Compound crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule.

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements.

The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(EAr) (Fc = Fe(η-CH)(η-CH); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles.