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

doi:10.1021/ja0041977

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

School of Science (Behrend)

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

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 language	English (US)
Pages (from-to)	8780-8784
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	123
Issue number	36
DOIs	https://doi.org/10.1021/ja0041977
State	Published - Sep 12 2001

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja0041977

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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, A. J., & 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

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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, {A. J.} and Takeuchi, {K. J.}",

year = "2001",

month = sep,

day = "12",

doi = "10.1021/ja0041977",

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volume = "123",

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journal = "Journal of the American Chemical Society",

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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

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, A. J.

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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DO - 10.1021/ja0041977

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C2 - 11535083

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SN - 0002-7863

VL - 123

SP - 8780

EP - 8784

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 36

ER -

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

Abstract

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