Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes

M. H.V. Huynh, J. M. Lasker, M. Wetzler, B. Mort, L. F. Szczepura, L. M. Witham, J. M. Cintron, A. C. Marschilok, L. J. Ackerman, R. K. Castellano, D. L. Jameson, M. R. Churchill, A. J. Jircitano, K. J. Takeuchi

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Abstract

The influence of two different di(1-pyrazolyl)alkane ligands on the rate constant of aqua ligand substitution of ruthenium(II) complexes with the formula [Ru(H2O)(L2)(tpmm)]2+ (L2 = di(1-pyrazolyl)methane (DPMet) or 2,2-di(1-pyrazolyl)propane (DPPro)) was investigated. A 9.4 × 105-fold increase in the rate constant of ligand substitution at pH = 6.86 was observed when DPMet was replaced with DPPro. This remarkable increase was unexpected, considering that these bidentate ligands appear quite similar. To help lend insight into this dramatic spectator ligand effect, the activation parameters for the ligand substitution reactions were determined, and single-crystal X-ray data were collected on the structurally analogous (chloro)ruthenium(II) complexes, [Ru(Cl)(L2)(tpmm)]+. These results are discussed in the context of a heteroscorpionate effect exerted by the DPPro ligand.

Original languageEnglish (US)
Pages (from-to)8780-8784
Number of pages5
JournalJournal of the American Chemical Society
Volume123
Issue number36
DOIs
StatePublished - Sep 12 2001

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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