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, Alan John Jircitano, K. J. Takeuchi

Research output: Contribution to journalArticle

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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

Fingerprint

Ruthenium
Rate constants
Substitution reactions
Ligands
Propane
Methane
Alkanes
Paraffins
Chemical activation
X-Rays
Single crystals
X rays

All Science Journal Classification (ASJC) codes

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

Cite this

Huynh, M. H. V., Lasker, J. M., Wetzler, M., Mort, B., Szczepura, L. F., Witham, L. M., ... Takeuchi, K. J. (2001). Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes. Journal of the American Chemical Society, 123(36), 8780-8784. https://doi.org/10.1021/ja0041977
Huynh, M. H.V. ; Lasker, J. M. ; Wetzler, M. ; Mort, B. ; Szczepura, L. F. ; Witham, L. M. ; Cintron, J. M. ; Marschilok, A. C. ; Ackerman, L. J. ; Castellano, R. K. ; Jameson, D. L. ; Churchill, M. R. ; Jircitano, Alan John ; Takeuchi, K. J. / Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 36. pp. 8780-8784.
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title = "Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes",
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.",
author = "Huynh, {M. H.V.} and Lasker, {J. M.} and M. Wetzler and B. Mort and Szczepura, {L. F.} and Witham, {L. M.} and Cintron, {J. M.} and Marschilok, {A. C.} and Ackerman, {L. J.} and Castellano, {R. K.} and Jameson, {D. L.} and Churchill, {M. R.} and Jircitano, {Alan John} and Takeuchi, {K. J.}",
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Huynh, MHV, Lasker, JM, Wetzler, M, Mort, B, Szczepura, LF, Witham, LM, Cintron, JM, Marschilok, AC, Ackerman, LJ, Castellano, RK, Jameson, DL, Churchill, MR, Jircitano, AJ & Takeuchi, KJ 2001, 'Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes', Journal of the American Chemical Society, vol. 123, no. 36, pp. 8780-8784. https://doi.org/10.1021/ja0041977

Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes. / Huynh, M. H.V.; Lasker, J. M.; Wetzler, M.; Mort, B.; Szczepura, L. F.; Witham, L. M.; Cintron, J. M.; Marschilok, A. C.; Ackerman, L. J.; Castellano, R. K.; Jameson, D. L.; Churchill, M. R.; Jircitano, Alan John; Takeuchi, K. J.

In: Journal of the American Chemical Society, Vol. 123, No. 36, 12.09.2001, p. 8780-8784.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Remarkable spectator ligand effect on the rate constant of ligand substitution of (Aqua)ruthenium(II) complexes

AU - Huynh, M. H.V.

AU - Lasker, J. M.

AU - Wetzler, M.

AU - Mort, B.

AU - Szczepura, L. F.

AU - Witham, L. M.

AU - Cintron, J. M.

AU - Marschilok, A. C.

AU - Ackerman, L. J.

AU - Castellano, R. K.

AU - Jameson, D. L.

AU - Churchill, M. R.

AU - Jircitano, Alan John

AU - Takeuchi, K. J.

PY - 2001/9/12

Y1 - 2001/9/12

N2 - 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.

AB - 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.

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U2 - 10.1021/ja0041977

DO - 10.1021/ja0041977

M3 - Article

VL - 123

SP - 8780

EP - 8784

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

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