Stereoisomerism of Dinuclear Molybdenum (V) Bis(2-ethylhexyl)dithiocarbamate Complexes
1984 Volume 1984 Issue 5 Pages 702-708
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1984 Volume 1984 Issue 5 Pages 702-708
The stereoisomerism of oxo- and thio-bridged dinuclear molybdenum(V) complexes, Mo2O2(μ-O, S)(S2CNR2)2[S1 complex], Mo2O2(μ-S)2(S2CNR2)2[S2complex], Mo2O2(μ-S)2(S2CNR2)2[S3 complex] and Mo2S2(μ-S)2(S2CNR2)2[S4 complex], where R is 2-ethylhexyl group, has been extensively investigated by HPLC, UV and IR techniques in connection with the chemical structure of MMo2O2(μ-S)2[S2CN(n-Bu)2]2 which was determined by X-ray crystallography in the previous paper.
On HPLC employing a Zorbax SIL column, the S1, S2 and S3 complexes gave five, five and three separable components, respectively, whereas the S4 complex showed a single peak. Two series of independent equilibrium relation existed among the five components of the 52 complex, one being cis-trans isomerism of the terminal oxygen atoms bound to the molybdenum atoms, and the other being isomerism due to the difference of a dihedral angle between two Mo(μ-S)2 planes. Therefore, the five components consist of three cis and two trans isomers as shown in Fig.5. The separation of these components by HPLC can be ascribed to the structural difference in the MoS2XS22+ cores rather than the variation in alkyl groups.
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