Half-sandwich 1,3-Di-t-butylcyclopentadienylRhodium Complexes Containing Sulfido Ligands

摘要

Treatment of 1,3-di-t-butylcyclopentadiene with rhodium trichloride in EtOHleads to the formation of binuclear half-sandwich complex [CptRhCl (μt-Cl)]2 (1) (Cpt = η5-tBu2CsH3) which reacts with trimethylphosphine to give CptRh(PMe3)C12(2) in high yield. 2reacts with ammonium polysulfide, (NH4)2Sx to give cyclooligosulfido half-sandwichcomplexes CptRh(PMe3)(Sn)(n=4(4a),6(4b)). Desulfurization of 4b by excess PPh3 resultsin cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convertcyclohexasulfido product 4b. The reaction of 2 with Et4NI gives diiodide complex 3 which isdetermined by single crystal X-ray crystallographic analysis.