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Complexes of the Platinum Metals. Part 30. Fragmentation Reactions of Rhodium and Iridium Trichloro- and Tribromo-acetates
Boyar, Esther B.,Robinson, Stephen D.
, p. 2113 - 2120 (2007/10/02)
The nitrosyl complexes (M = Rh or Ir) react readily with trichloroacetic acid in acetone solution at ambient temperature to afford the dichloro-complexes in excellent yield.The rhodium-based reaction performed at ca. 0 deg C and quickly worked-up affords the carboxylate complex which is stable in pure acetone, but rapidly converts to the dichloride when free trichloroacetic acid and triphenylphosphine are introduced to the solution.The complexes , , mer-, and also react with trichloroacetic acid to form trichloroacetates which undergo similar ligand fragmentation reactions.Reaction pathways involving formation of CCl3(1-), Cl(1-), :CCl2, and CO2 fragments are outlined; hydrolysis of dichlorocarbene affords carbonyl ligands.Similar reactions have been observed with tribromoacetic acid.
