Steric Ligand Effects of Six Bidentate Bipyridyl Ligands

Carol A. Bessel, Joseph A. Margarucci, J. Henry Acquaye, Robert S. Rubino, Janet Crandall, Alan J. Jircitano, Kenneth J. Takeuchi

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Abstract

The synthesis and characterization of a series of [Ru(H2O)(N-N)(trpy)]2+ complexes (where N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen), 2,2′-biquinoline (biq), and 6,6′-dichloro-2,2′-bipyridine (6,6′-Cl2bpy), and trpy = 2,2′: 6′,2″-terpyridine) are described. The rate constants for ligand substitution of the aqua ligand for acetonitrile were determined for the [Ru(H2O) (N-N) (trpy)]2+ complexes as well as for a series of [Ru(H2O)(bpy)2(PR3)]2+ complexes in pH = 2.2 HNO3/NaNO3 (μ = 0.1) solution at 25 °C. The electronic (E) and steric (S) properties of the phopshine ligands in the [Ru(H2O)(bpy)2(PR3)]2+ complexes correlated well with the rate constants for ligand substitution (kls) using the relationship In kls = aE + bS + c (where a–c are constants which were determined by linear regression analyses). The equation for the [Ru(H2O)(bpy)2(PR3)]2+ complexes was used to calculate the cone angles of the six bidentate bipyridyl ligands (N-N). These cone angles represent the first quantitative estimates of steric ligand effects for bidentate bipyridyl ligands.

Original languageEnglish (US)
Pages (from-to)5779-5784
Number of pages6
JournalInorganic chemistry
Volume32
Issue number25
DOIs
StatePublished - Jan 1 1993

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2,2'-Dipyridyl
Ligands
ligands
Cones
Rate constants
cones
Substitution reactions
substitutes
Linear regression
acetonitrile
regression analysis
synthesis
estimates
electronics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Bessel, C. A., Margarucci, J. A., Acquaye, J. H., Rubino, R. S., Crandall, J., Jircitano, A. J., & Takeuchi, K. J. (1993). Steric Ligand Effects of Six Bidentate Bipyridyl Ligands. Inorganic chemistry, 32(25), 5779-5784. https://doi.org/10.1021/ic00077a021
Bessel, Carol A. ; Margarucci, Joseph A. ; Acquaye, J. Henry ; Rubino, Robert S. ; Crandall, Janet ; Jircitano, Alan J. ; Takeuchi, Kenneth J. / Steric Ligand Effects of Six Bidentate Bipyridyl Ligands. In: Inorganic chemistry. 1993 ; Vol. 32, No. 25. pp. 5779-5784.
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abstract = "The synthesis and characterization of a series of [Ru(H2O)(N-N)(trpy)]2+ complexes (where N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen), 2,2′-biquinoline (biq), and 6,6′-dichloro-2,2′-bipyridine (6,6′-Cl2bpy), and trpy = 2,2′: 6′,2″-terpyridine) are described. The rate constants for ligand substitution of the aqua ligand for acetonitrile were determined for the [Ru(H2O) (N-N) (trpy)]2+ complexes as well as for a series of [Ru(H2O)(bpy)2(PR3)]2+ complexes in pH = 2.2 HNO3/NaNO3 (μ = 0.1) solution at 25 °C. The electronic (E) and steric (S) properties of the phopshine ligands in the [Ru(H2O)(bpy)2(PR3)]2+ complexes correlated well with the rate constants for ligand substitution (kls) using the relationship In kls = aE + bS + c (where a–c are constants which were determined by linear regression analyses). The equation for the [Ru(H2O)(bpy)2(PR3)]2+ complexes was used to calculate the cone angles of the six bidentate bipyridyl ligands (N-N). These cone angles represent the first quantitative estimates of steric ligand effects for bidentate bipyridyl ligands.",
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Bessel, CA, Margarucci, JA, Acquaye, JH, Rubino, RS, Crandall, J, Jircitano, AJ & Takeuchi, KJ 1993, 'Steric Ligand Effects of Six Bidentate Bipyridyl Ligands', Inorganic chemistry, vol. 32, no. 25, pp. 5779-5784. https://doi.org/10.1021/ic00077a021

Steric Ligand Effects of Six Bidentate Bipyridyl Ligands. / Bessel, Carol A.; Margarucci, Joseph A.; Acquaye, J. Henry; Rubino, Robert S.; Crandall, Janet; Jircitano, Alan J.; Takeuchi, Kenneth J.

In: Inorganic chemistry, Vol. 32, No. 25, 01.01.1993, p. 5779-5784.

Research output: Contribution to journalArticle

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T1 - Steric Ligand Effects of Six Bidentate Bipyridyl Ligands

AU - Bessel, Carol A.

AU - Margarucci, Joseph A.

AU - Acquaye, J. Henry

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AU - Jircitano, Alan J.

AU - Takeuchi, Kenneth J.

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N2 - The synthesis and characterization of a series of [Ru(H2O)(N-N)(trpy)]2+ complexes (where N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen), 2,2′-biquinoline (biq), and 6,6′-dichloro-2,2′-bipyridine (6,6′-Cl2bpy), and trpy = 2,2′: 6′,2″-terpyridine) are described. The rate constants for ligand substitution of the aqua ligand for acetonitrile were determined for the [Ru(H2O) (N-N) (trpy)]2+ complexes as well as for a series of [Ru(H2O)(bpy)2(PR3)]2+ complexes in pH = 2.2 HNO3/NaNO3 (μ = 0.1) solution at 25 °C. The electronic (E) and steric (S) properties of the phopshine ligands in the [Ru(H2O)(bpy)2(PR3)]2+ complexes correlated well with the rate constants for ligand substitution (kls) using the relationship In kls = aE + bS + c (where a–c are constants which were determined by linear regression analyses). The equation for the [Ru(H2O)(bpy)2(PR3)]2+ complexes was used to calculate the cone angles of the six bidentate bipyridyl ligands (N-N). These cone angles represent the first quantitative estimates of steric ligand effects for bidentate bipyridyl ligands.

AB - The synthesis and characterization of a series of [Ru(H2O)(N-N)(trpy)]2+ complexes (where N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen), 2,2′-biquinoline (biq), and 6,6′-dichloro-2,2′-bipyridine (6,6′-Cl2bpy), and trpy = 2,2′: 6′,2″-terpyridine) are described. The rate constants for ligand substitution of the aqua ligand for acetonitrile were determined for the [Ru(H2O) (N-N) (trpy)]2+ complexes as well as for a series of [Ru(H2O)(bpy)2(PR3)]2+ complexes in pH = 2.2 HNO3/NaNO3 (μ = 0.1) solution at 25 °C. The electronic (E) and steric (S) properties of the phopshine ligands in the [Ru(H2O)(bpy)2(PR3)]2+ complexes correlated well with the rate constants for ligand substitution (kls) using the relationship In kls = aE + bS + c (where a–c are constants which were determined by linear regression analyses). The equation for the [Ru(H2O)(bpy)2(PR3)]2+ complexes was used to calculate the cone angles of the six bidentate bipyridyl ligands (N-N). These cone angles represent the first quantitative estimates of steric ligand effects for bidentate bipyridyl ligands.

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Bessel CA, Margarucci JA, Acquaye JH, Rubino RS, Crandall J, Jircitano AJ et al. Steric Ligand Effects of Six Bidentate Bipyridyl Ligands. Inorganic chemistry. 1993 Jan 1;32(25):5779-5784. https://doi.org/10.1021/ic00077a021