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)[eta (5)-C5H4C(O)CH2CH2CO2Me]}(-) with RuC o2(CO)(9)(mu (3)-Se) in THF at 60 degreesC gave two new cluster derivatives (mu (3)-Se)CoMRu(CO)(8)[eta (5)-C5H4C(O)CH2CH2CO2Me] (M = Mo 1, M = W 2). Similarly, reactions of dianions (-){M(CO)(3)[(eta (5)-C5H4)C(O)CH2CH2C(O)( eta (5)-C5H4)](CO)(3)M}(-) with two molecules of RuCo2(CO)(9)(mu (3)-Se) ga ve 1,4-succinoyl(biscyclopentadienyl)-bridged double cluster complexes (mu (3)-Se)CoMRu(CO)(8)[eta (5)-C5H4)C(O)CH2CH2C(O)(eta (5)-C5H4)]CoMRu(CO)(8)( mu (3)-Se) (M=Mo 3, M=W 4). Treatment of cluster (mu (3)-Se)CoMoRu(CO)(8)[( eta (5)-C5H4)C(O)Me] with ammine derivatives 2,4-dinitrophenylhydrazine, NH 2NHC(S)NH2, (-)-5-(alpha -phenyl)semioxamazide and L-(+)-menthydrazide, res pectively, at room temperature produced four new hydrazone cluster derivati ves (mu (3)-Se)CoMoRu(CO)(8)[eta (5)-C5H4C(NR)Me] (R=NHC6H3-2,4-(NO2)(2) 5, R = NHC(S)NH2 6, R = NHC(O)C(O)NHCH(Me)(C6H5) 7, R = NHCO2-menthyl 8). How ever, cluster 1 can only react with 2,4-dinitrophenylhydrazine to give the formation of cluster (mu (3)-Se)CoMoRu(CO)(8)[eta (5)-C5H4C(NR)CH2CH2CO2Me] (R = NHC6H3-2,4-(NO2)(2) 9) under similar condition. Although, two kinds o f optically active groups have been introduced into cluster (mu (3)-Se)CoMo Ru(CO)(8)[(eta (5)-C5H4)C(O)Me], the mixture of diastereoisomers could not be separated by silica gel chromatography. The C-13-NMR spectra showed the presence of a pair of diastereoisomers. (C) 2001 Elsevier Science B.V. All rights reserved.