Treatment of ferrocene with mercuric trifluoroacetate (10 equiv) and mercuric oxide (5 equiv) in 1:1 diethyl ether/ethanol afforded decakis[(trifluoroacetoxy)mercurio]ferrocene (60%) as a yellow-orange powder. Reaction with cupric chloride dihydrate in acetone yielded mixtures of partially chlorinated ferrocenes, of which decachloroferrocene was a minor component. Treatment of ferrocene with mercuric acetate (10 equiv) in refluxing dichloroethane for 18 h afforded decakis(acetoxymercurio)ferrocene (95%). Halogenation of decakis(acetoxymercurio)ferrocene with cupric chloride dihydrate in acetone, potassium tribromide in water, or potassium triiodide in water afforded decachloroferrocene (27%), decabromoferrocene (60%), and decaiodoferrocene (67%), respectively. Examination of the H-1 NMR spectra of crude decachloroferrocene and decabromoferrocene revealed small amounts (less-than-or-equal-to 5%) of partially halogenated ferrocenes, which suggested that decakis(acetoxymercurio)ferrocene was not completely decamercurated. Treatment of ruthenocene with mercuric acetate (10 equiv) in refluxing dichloroethane afforded decakis(acetoxymercurio)ruthenocene (88%). Reaction of decakis(acetoxymercurio)ruthenocene with cupric chloride dihydrate in acetone, potassium tribromide in water, or potassium triiodide in water afforded decachlororuthenocene (73%), decabromoruthenocene (47%), and decaiodoruthenocene (39%), respectively. Inspection of the H-1 NMR spectra of crude decachlororuthenocene and decabromoruthenocene showed no resonances that could be attributed to partially halogenated ruthenocenes, which indicates that decakis(acetoxymercurio)ruthenocene was greater-than-or-equal-to 98% decamercurated. Treatment of pentamethylruthenocene with mercuric acetate in 1:1 diethyl ether/ethanol afforded pentakis(acetoxymercurio)pentamethylruthenocene (88%). Pentakis(acetoxymercurio)pentamethylruthenocene showed hindered rotation of the mercury-acetate groups in the H-1 NMR spectra. Halogenation afforded pentachloropentamethylruthenocene (67%), pentabromopentamethylruthenocene (35%), and pentaiodopentamethylruthenocene (60%). Treatment of (eta5-pentamethylcyclopentadienyl)(eta5-indenyl)ruthenium(II) with mercuric acetate (greater-than-or-equal-to 3 equiv) in 1:1 diethyl ether-ethanol afforded (eta5-1,2,3-tris(acetoxYmercurio)indenyl)(eta5-pentamethylcyclopentadienyl)ruthenium(II) (99%), which could be brominated and iodinated to afford (eta5-1,2,3-tribromoindenyl)(eta5-pentamethylcyclopentadienyl) ruthenium(II) (29%) and (eta5-1,2,3-triiodoindenyl)(eta5-pentamethylcyclopentadienyl)r uthenium(II) (66%). The structure of (eta5-1,2,3-triiodoindenyl)(eta5-pentamethylcyclopentadienyl)r uthenium(II) was determined, showing that it crystallized in the monoclinic space group P2(1)/c with cell dimensions a 15.934(3) angstrom, b = 10.308(4) angstrom, c = 12.530 (5) angstrom, beta = 93.53(2)-degrees, V = 2054(1) angstrom3, and Z = 4.
