- The Oxidative Demethylation of Tertiary Amines by Oxo(phosphine)ruthenium(IV) Complexes
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The oxidation of para-substituted N,N-dimethylanilines by oxo(phosphine)ruthenium(IV) complexes is shown to display cytochrome P-450-like reactivity, where tertiary amines are oxidatively dealkylated, yielding the corresponding N-methylaniline and formaldehyde.
- Leising, Randolph A.,Ohman, Jeffrey S.,Acquaye, John H.,Takeuchi Kenneth J.
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- Steric ligand effects of six bidentate bipyridyl ligands
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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 ln 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.
- Bessel, Carol A.,Margarucci, Joseph A.,Acquaye, J. Henry,Rubino, Robert S.,Crandall, Janet,Jircitano, Alan J.,Takeuchi, Kenneth J.
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p. 5779 - 5784
(2008/10/08)
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