42071-43-2Relevant academic research and scientific papers
Ru(CH3CN)3Cl3, preparation and use as a mediator for the electrooxidation of hydrocarbons
Appelbaum,Heinrichs,Demtschuk,Michman,Oron,Schaefer,Schumann
, p. 240 - 250 (1999)
Hydrogenation of ruthenium chloride in acetonitrile yields complexes of the type Ru(CH3CN)nCl6-n of which three are isolated (n=2, 3, 4). Their formation is traced by voltammetry. Ru(CH3CN)2Cl4 and Ru(CH3CN)3Cl3 have been characterized by single-crystal X-ray diffraction. Voltammetry shows that Ru(CH3CN)3Cl3 acts as a mediator for oxidation of cyclohexene, methylcyclohexene, 1-tetralol and tetralin. Its role in tetralin oxidation is illustrated by preparative scale electrolysis. The compounds Ru(CH3CN)2Cl4 and Ru(CH3CN)4Cl2 did not react with any of the mentioned hydrocarbons.
Homogeneous catalysis and selectivity in electrochemistry
Michman, Michael,Appelbaum, Lina,Gun, Jenny,Modestov, Alexander D.,Lev, Ovadia
, p. 4729 - 4737 (2015/04/27)
The relationship between homogeneous catalysis and electrochemistry is examined in light of two examples based on our work concerning (a) catalyst activation, regarding selective electrochemical C-H oxidation with RuIII/RuIV mediation, and (b) catalyst suppression, regarding controlling selectivity in electrochemical aromatic chlorination. The first example (a) deals with the role of catalysis at the working electrode. The electrochemical (EC) oxidation of specific hydrocarbons such as tetralin and indane is performed using tris(acetonitrile)ruthenium trichloride (Ru(CH3CN)3Cl3) as a mediator. The role of this mediator in the oxidation of tetralin has been reported. This homogeneous C-H activation by electron transfer (ET) is accompanied by the redox transitions of the mediator in the course of the catalytic oxidation, and these are the main points of interest here. Additional studies with a rotating ring disk electrode (RRDE) provided a follow-up of creation and recovery of RuIII/RuII and RuIII/RuIV species in the process. Using electrochemistry linked with electrospray ionization mass spectrometry (EC/ESI-MS) gave additional information on the structure of the reduced and oxidized forms of Ru(CH3CN)3Cl3 and the effect of water in the solvent on their lifetimes. The second example (b) of electrochlorination has been reported elsewhere and is brought up as complementary remarks. Aromatic electrophilic chlorination of 1,4-dimethoxy-2-tertbutylbenzene is autocatalyzed and unselective. The EC procedure provides a simple means to inhibit the catalytic runaway reaction. This example shows how the counter electrode affects catalysis and selectivity. (Figure Presented)
