Synthesis, characterization and reactions of cluster complexes containing SeRuCoM (M=Mo or W) core and a functionally substituted cyclopentadienyl ligand

Reactions of monoanions {M(CO)3[η5-C5H4C(O)CH2CH2CO2Me]}− with RuCo2(CO)9(μ3-Se) in THF at 60°C gave two new cluster derivatives (μ3-Se)CoMRu(CO)8[η5-C5H4C(O)CH2CH2CO2Me] (M=Mo 1, M=W 2). Similarly, reactions of dianions −{M(CO)3[(η5-C5H4)C(O)CH2CH2C(O)(η5-C5H4)](CO)3M}− with two molecules of RuCo2(CO)9(μ3-Se) gave 1,4-succinoyl(biscyclopentadienyl)-bridged double cluster complexes (μ3-Se)CoMRu(CO)8[(η5-C5H4)C(O)CH2CH2C(O)(η5-C5H4)]CoMRu(CO)8(μ3-Se) (M=Mo 3, M=W 4). Treatment of cluster (μ3-Se)CoMoRu(CO)8[(η5-C5H4)C(O)Me] with ammine derivatives 2,4-dinitrophenylhydrazine, NH2NHC(S)NH2, (−)-5-(α-phenyl)semioxamazide and l-(+)-menthydrazide, respectively, at room temperature produced four new hydrazone cluster derivatives (μ3-Se)CoMoRu(CO)8[η5-C5H4C(NR)Me] (R=NHC6H3-2,4-(NO2)25, R=NHC(S)NH26, R=NHC(O)C(O)NHCH(Me)(C6H5) 7, R=NHCO2-menthyl 8). However, cluster 1 can only react with 2,4-dinitrophenylhydrazine to give the formation of cluster (μ3-Se)CoMoRu(CO)8[η5-C5H4C(NR)CH2CH2CO2Me] (R=NHC6H3-2,4-(NO2)29) under similar condition. Although, two kinds of optically active groups have been introduced into cluster (μ3-Se)CoMoRu(CO)8[(η5-C5H4)C(O)Me], the mixture of diastereoisomers could not be separated by silica gel chromatography. The 13C-NMR spectra showed the presence of a pair of diastereoisomers.