REACTIONS OF THE PENTANUCLEAR MIXED-METAL CLUSTER COMPOUND [RU4RHC(CO)12(ETA(5)-C5ME5)] - SYNTHESIS, CHARACTERIZATION AND CRYSTAL-STRUCTURE OF THE PENTANUCLEAR DERIVATIVE [RU4RHC(CO)11H(ETA(5)-C5ME5)I]

Treatment of the pentanuclear cluster [Ru4RhC(CO)12(eta5-C5Me5)] 1 with an excess of [NEt4][BH4] yielded the monoanion [Ru4RhC(CO)11H (eta5-C5Me5)] - which has been isolated as its [NEt4]+ salt 2. Reaction of the monoanion with iodine solution gave the novel derivative [Ru4RhC(CO)11H(eta5-C5Me5)I] 3. Compound 3 crystallises in the monoclinic space group P2(1)/n with a = 1 5.243(3), b = 18.683(3), c = 10.425(2) angstrom, beta = 90.0(2)-degrees. The five metal atoms adopt a wingtip-bridged butterfly arrangement with the rhodium forming one of the 'hinge' atoms [Ru-Ru 2.816(1)-2.899(1), Ru-Rh 2.816(1)-2.826(1) Al. The parent cluster [Ru4RhC(CO)12(eta5-C5Me5)] 1 reacted at room temperature with the neutral ligands P(OMe)3 and PPh3 to yield compounds [Ru4RhC(CO)10{P(OMe)3}2(eta5-C5Me5)] 4 (three isomers) and (Ru4RhC(CO)10(PPh3)2(eta5-C5Me5)] 5. Compound 1 reacts with [N(PPh3)2]Cl to yield the adduct [Ru4RhC(CO)12(eta5-C5Me5)Cl]- which on protonation produces [Ru4RhC(CO)12H(eta5-C5Me5)Cl] 6.