Preparation, separation, and characterization of ruthenium(II) thiocyanate linkage isomers |
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Authors: | Vandenburgh Lucas Buck Matthew R Freedman Daniel A |
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Institution: | Chemistry Department, The State University of New York at New Paltz, 1 Hawk Drive, New Paltz, New York 12561, USA. |
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Abstract: | The reaction of (p-cym)Ru(bpy)Cl](+) (p-cym = eta(6)-p-cymene; bpy = 2,2'-bipyridine) with SCN(-) gives a mixture of the linkage isomers (p-cym)Ru(bpy)(SCN)](+) and (p-cym)Ru(bpy)(NCS)](+). The linkage isomers were efficiently separated by column chromatography on Hg(NO3)2-coated Al2O3. Both isomers were fully characterized by elemental analysis, (1)H NMR and IR spectroscopy, and X-ray crystallography. The equilibrium constant for the conversion of the S-bound to the N-bound isomer was determined to be 0.29(4) in methanol-d4 and 0.74(7) in acetone-d6, respectively, at 50 degrees C. Kinetic data for the linkage isomerization reaction are also reported. |
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