The electrochemical reduction of H4Ru4(CO)(12) in tetrahydrofuran (THF) is studied by means of de and ac polarography, cyclic voltammetry, and FT-IR spectroscopy following electrolysis in a optically transparent thin-layer electrochemical (OTTLE) cell. The reduction of the title complex generates a transient radical anion, [H4Ru4(CO)(12)](-), which produces the stable anion [H3Ru4(CO)(12)](-) On a longer time scale. In the presence of triphenylphosphine, nucleophilic substitutions readily take place by electrochemical initiation and produce mono- and bisubstituted derivatives in yields depending on PPh(3) concentration. The termination side chain reaction is the loss of a hydride ligand, to give the above-mentioned anion, which is inert to substitution even in the presence of a large excess of Lewis base.

Electrochemical-Behavior And Electron-Transfer Chain (Etc) Reactions Of H4ru4(Co)(12)

OSELLA, Domenico;NERVI, Carlo;RAVERA, Mauro;
1995

Abstract

The electrochemical reduction of H4Ru4(CO)(12) in tetrahydrofuran (THF) is studied by means of de and ac polarography, cyclic voltammetry, and FT-IR spectroscopy following electrolysis in a optically transparent thin-layer electrochemical (OTTLE) cell. The reduction of the title complex generates a transient radical anion, [H4Ru4(CO)(12)](-), which produces the stable anion [H3Ru4(CO)(12)](-) On a longer time scale. In the presence of triphenylphosphine, nucleophilic substitutions readily take place by electrochemical initiation and produce mono- and bisubstituted derivatives in yields depending on PPh(3) concentration. The termination side chain reaction is the loss of a hydride ligand, to give the above-mentioned anion, which is inert to substitution even in the presence of a large excess of Lewis base.
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CLUSTER CHEMISTRY; CARBONYL CLUSTERS; RUTHENIUM; DERIVATIVES; FERROCENE; OSMIUM; IRON
D. OSELLA; C. NERVI; M. RAVERA; J. FIEDLER; V. V. STRELETS
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/45008
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