Tetraruthenium carbonyl complexes containing germyl and stannyl ligands from the reactions of Ru4(CO)13(μ-H)2 with HGePh3 and HSnPh3

The compounds Ru4(CO)12(GePh3)2(μ-H)4, 1 and Ru4(CO)12(SnPh3)2(μ-H)4, 2 were obtained from the reactions of Ru4(CO)13(μ-H)2 with HGePh3 and HSnPh3, respectively. Both compounds contain a nearly planar butterfly structure for the four metal atoms with two GePh3/SnPh3 ligands and four bridging hydride ligands around the periphery of the cluster. When heated, 1 and 2 were converted into the complexes Ru4(CO)12(μ4-EPh)2, 3, E = Ge, and 4, E = Sn, by cleavage of two phenyl groups from each of the GePh3 ligands. Compounds 3 and 4 contain square planar arrangements of the four ruthenium atoms with quadruply bridging germylyne and stannylyne ligands on opposite sides of the square plane. The bonding and electronic transitions of 3 were analyzed by DFT computational analyses.