Synthesis, Electrochemistry, and Reactivities of trans-VI(L)O2>2+ (L = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propylenediamine)

DOI: 10.1039/DT9900003735

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3735 - 3739 (1990)

Update date:2022-08-11

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Authors:

Che, Chi-Ming

Tang, Wai-Tong

Li, Chi-Keung

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Article abstract of DOI:10.1039/DT9900003735

The synthesis and characterization of the ligand N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propylenediamine (L) and the complex trans-VI(L)O2>2+ are described.The complex has been characterized by u.v.-visible xy -> d_?* (d_?* = d_xz,d_yz) at 380-420 nm> and i.r. <ν_asym(RuO2) at 860 cm^-1> spectroscopy.At pH 1.0 it exhibits three reversible couples Ru^VI-Ru^IV, Ru^IV-Ru^III, and Ru^III-Ru^II at potentials of 0.89, 0.60, and 0.28 V respectively vs. saturated calomel electrode.The Ru^VI-Ru^IV couple splits into two reversible one-electron couples Ru^VI-Ru^V and Ru^V-Ru^IV in alkaline solutions (pH > 9).The complex is a powerful oxidant, capable of oxidizing toluene to benzaldehyde, alcohols to aldehydes/ketones, tetrahydrofuran to γ-butyrolactone, and norbornene to exo-2,3-epoxynorbornane in high yields at room temperature.Oxidation of cis- and trans-stilbenes gave benzaldehyde and trans-stilbene oxides.