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Thiocyanate linkage isomerism in the isobutyl ester form of the ruthenium dye known as N3

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Using a modification of a recently reported convenient synthesis of the isobutyl ester form of the bis(isothiocyanato) ruthenium dye (N3), we report the isolation and spectroscopic characterization of the minor isomer in which one NCS is N-bound and the other is S-bound. The synthesis involves the reaction of Ru(iBu2dcbpy)2Cl2, where iBu2dcbpy is the diisobutyl ester of 4,4′-dicarboxy-2,2′-bipyridine, with a source of thiocyanate. The impact of the isocyanate salt, solvent, and temperature on the yield of the linkage isomers is presented. In addition to the two linkage isomers 1 and 2, the partially substituted chloroisothiocyanato complex 3, Ru(iBu2dcbpy)2Cl(NCS), was also isolated. Selective removal of the chloride using silver triflate provided a path to [Ru(iBu2dcbpy)2(pyridine)(NCS)]OTf, 4, in high yield. The complexes were characterized by 1H and 13C NMR, IR, and electronic absorption spectroscopies and mass spectrometry. At 80 °C in DMSO-d6, the isomerization of 2 to 1 is complete and exhibits first-order kinetics with a rate constant of 0.00014 s−1. Room temperature hydrolysis of the isobutyl ester groups of 2 using [nBu4 N]OH in acetonitrile produced a mixture of the two linkage isomers.
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Keywords: Bipyridine; Isocyanate; Linkage isomerism; N3; Ruthenium

Document Type: Research Article

Affiliations: Department of Chemistry, University of Minnesota, Minneapolis, MN, USA

Publication date: January 2, 2014

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