UBC Theses and Dissertations
Some reactions of 1,2,3-trithia--ferrocenophanes Talaba, Ana
The ability of l,2,3-trithia--ferrocenophane and (N,N-dimethylaminomethyl)-l,2,3-trithia--ferrocenophane to function as ligands towards transition metals of groups 7 and 8 was explored. Thermal reactions of l,2,3-trithia--ferrocenophane with ruthenium and osmium carbonyls produced 18-electron ferrocenedithiolato ruthenium and osmium carbonyl complexes isolated in low (5-10%) or moderate yields (25-35%). The ruthenium and osmium complexes, Fe(η⁵-C₅H₄S)₂Ru₂(CO)₆ and Fe(η⁵-C₅H₄S)₂(μ₃-S)(μ-CO)₂Os₄(CO)₉, were characterized by X-ray crystallographic analysis. The crystal structure of the ruthenium complex reveals a very distorted octahedral coordination about the ruthenium atoms and a Ru-Ru separation of 2.6812(7) Å which is comparable to the lengths found in other ruthenium(I) dimers. The structure of the osmium cluster compound reveals a spiked triangular configuration of osmium atoms with a sulfido ligand triply bridging the osmium triangle and the C₅H₄S ligands doubly bridging the spike Os-Os bond. Both structures have eclipsed and nearly parallel cyclopentadienyl rings. Reactions of l,2,3-trithia--ferrocenophane with cobalt and manganese carbonyls produced unidentified insoluble solids, in high yields. Two low yield soluble cobalt derivatives Fe(η⁵-C₅H₄S)₂Co₂(CO)₆ and Fe(η⁵-C₅H₄)₂Co₄(CO)₁₂, and a paramagnetic manganese derivative were also isolated from these reactions. Reactions of (N,N-dimemylammomethyl)-l,2,3-trithia--ferrocenophane with ruthenium and iron carbonyls, and some rhodium and palladium complexes afforded oils and solids which were not identified. These products are insoluble in common organic solvents and are produced in yields varying from 20 to 90 %. Microanalytical data indicate that the products are not analytically pure compounds. A soluble iron derivative isolated in trace quantity, was identified from the fragments exhibited by the low-resolution spectrum as [Fe(C₅H₄S₂)(C₅H₃CH₂NMe₂)]₂Fe₂(CO)₆.
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