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

Chemistry

SUNY Buffalo
Los Alamos National Laboratory
Illinois State University
Gettysburg College
Pennsylvania State University

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

20 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
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

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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

@article{d7bf292a660b4220a16afb1fcc6c8595,

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",

language = "English",

volume = "123",

pages = "8780--8784",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "36",

}

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.

UR - https://www.scopus.com/pages/publications/0035850498

U2 - 10.1021/ja0041977

DO - 10.1021/ja0041977

M3 - Article

C2 - 11535083

AN - SCOPUS:0035850498

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

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