Reaction of CH2(Ph2PSe)2 (dppmSe2) with [Ru3(CO)12]. Fluxional behaviour of [Ru3(µ3-Se)2(CO)7(µ-dppm)] and crystal structures of [Ru4(µ4-Se)2(µ-CO)(CO)8(µ-dppm)]·MeOH and [Ru6(µ3-Se)4(CO)12(µ-dppm)2]·CH2Cl2

The reaction of [Ru3(CO)12] with dppmSe2 afforded the open-triangular nido cluster [Ru3(µ3-Se)2(CO)7(µ-dppm)] 1, the closo-octahedral species [Ru4(µ4-Se)2(µ-CO)(CO)8(µ-dppm)] 2 and the cubane-like cage [Ru4(µ3-Se)4(CO)10(µ-dppm)] 3. Multinuclear NMR data indicated a fluxional behaviour for 1 in solution consisting both in the reversible migration of a metal–metal bond in the cluster and in the oscillation of the methylene group of the dppm ligand. Pyrolysis of 1 gave the condensation derivative [Ru6(µ3-Se)4(CO)12(µ-dppm)2] containing a central 64-electron butterfly core.

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