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(iBu 2dcbpy)2Cl(NCS), was also isolated. Selective removal of the chloride using silver triflate provided a path to [Ru(iBu 2dcbpy)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.

Original languageEnglish (US)
Pages (from-to)17-28
Number of pages12
JournalJournal of Coordination Chemistry
Issue number1
StatePublished - Jan 2 2014

Bibliographical note

Funding Information:
This work is funded by a grant from the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy under Award Number DE-FG02-07ER15913.


  • Bipyridine
  • Isocyanate
  • Linkage isomerism
  • N3
  • Ruthenium


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