PENTAMERCURATION OF CYCLOPENTADIENYLMANGANESE TRICARBONYL AND CYCLOPENTADIENYLRHENIUM TRICARBONYL - CRYSTAL-STRUCTURE OF (PENTAIODOCYCLOPENTADIENYL)MANGANESE TRICARBONYL

Treatment of cyclopentadienylmanganese tricarbonyl and cyclopentadienylrhenium tricarbonyl with mercuric acetate (5 equiv) in refluxing 1,2-dichloroethane for 4 h afforded pentakis-(acetoxymercurio)cyclopentadienyl)manganese tricarbonyl (73%) and (pentakis(acetoxymercurio)cyclopentadienyl)rhenium tricarbonyl (90%) as pale yellow powders. These new complexes were characterized by H-1 NMR, infrared spectroscopy, and microanalysis. Reaction of (pentakis(acetoxymercurio)cyclopentadienyl)manganese tricarbonyl with cupric chloride in refluxing acetone, cupric bromide in refluxing acetone, and potassium triiodide in water afforded (pentachlorocyclopentadienyl)manganese tricarbonyl (45%), (pentabromocyclopentadienyl)manganese tricarbonyl (44%), and (pentaiodocyclopentadienyl)manganese tricarbonyl (19%). Treatment of (pentakis(acetoxymercurio)cyclopentadienyl)rhenium tricarbonyl with the above halogenating agents afforded only unidentified decomposition products. The structure of (pentaiodocyclopentadienyl)manganese tricarbonyl was determined, showing that this compound crystallized in the triclinic space group P1BAR, with cell dimensions a = 13.547(4) angstrom, b = 14.360(3) angstrom, c = 16.729(4) angstrom, alpha = 90.95(2)-degrees, beta = 89.91(2)-degrees, gamma = 103.77(2)-degrees, V = 3160(l) angstrom3, and Z = 8.