Synthesis, reaction and enantiomeric resolution of chiral clusters containing SRuNiM (M=Mo, W) core

The treatment of [(η5-C5H4R)CoRuM(CO)8(μ3-S)] with NiCp2 in THF at refluxing temperature gives six novel clusters containing functionally substituted cyclopentadienyl ligand [(η5-C5H5)(η5-C5H4COR)NiRuM(CO)5(μ3-S)] (1, M=Mo, R=CH3; 2, M=W, R=CH3; 3, M=Mo, R=OC2H5; 4, M=W, R=OC2H5; 5, M=Mo, R=COC6H4COOCH3; 6 M=W, R=COC6H4COOCH3). The reactions of clusters (1–6) with 2,4-dinitrophenylhydrazine were investigated. The ester group was difficult to hydrolyze (clusters 3–6). Hydrazide can easily condense with the ketonic carbonyl (cluster 1 and 2) on the cyclopentadienyl ring to form complexes [(η5-C5H5)(η5-C5H4C(NR)CH3)NiRuM(CO)5(μ3-S)] (7, M=Mo, R=NH-C6H3-2,4-(NO2)2; 8, M=W, R=NHC6H3-2,4-(NO2)2). The structures of 1, 2 and 7 have been established by the single crystal X-ray diffraction method and the enantiomers of chiral complexes 1, 3 and 5 were successfully separated by liquid chromatography.