The dimethylaminopyridine (DMAP) promoted reaction between [Os(bpy)(2)(CO)(OTf)]OTf (where OTf = CF3SO3-) and methylene chloride is reported. C-Cl bond breaking of a solvent molecule leads to the formation of the [Os(bpy)(2)(CO)(Cl)]OTf complex. The reactivity and redox properties of [Os(bpy)(2)(CO)(OTf)]OTf were investigated by means of room- and low-temperature electrochemical experiments. In CH2Cl2, at low temperature, the complex undergoes two le electrochemical and chemical reversible reductions (ErEr mechanism), but at room temperature a more complex electrochemical mechanism is observed, leading to the electro-synthesis of [Os(bpy)(2)(CO)(Cl)]OTf via electrochemical reversible and chemical irreversible reduction processes (ErCi mechanism). The DMAP nucleophilicity was used to produce the new [Os(bpy)(2)(CO)(Br)]OTf and [Os(bpy)(2)(CO)(I)]OTf complexes which have been fully characterized. (C) 2004 Elsevier B.V. All rights reserved.

Electrochemical behaviour and reactivity of [Os(bpy)(2)(CO)(OTf)](+) in halogenated solvents

GARINO, Claudio;GOBETTO, Roberto;NERVI, Carlo;SALASSA, LUCA
2005

Abstract

The dimethylaminopyridine (DMAP) promoted reaction between [Os(bpy)(2)(CO)(OTf)]OTf (where OTf = CF3SO3-) and methylene chloride is reported. C-Cl bond breaking of a solvent molecule leads to the formation of the [Os(bpy)(2)(CO)(Cl)]OTf complex. The reactivity and redox properties of [Os(bpy)(2)(CO)(OTf)]OTf were investigated by means of room- and low-temperature electrochemical experiments. In CH2Cl2, at low temperature, the complex undergoes two le electrochemical and chemical reversible reductions (ErEr mechanism), but at room temperature a more complex electrochemical mechanism is observed, leading to the electro-synthesis of [Os(bpy)(2)(CO)(Cl)]OTf via electrochemical reversible and chemical irreversible reduction processes (ErCi mechanism). The DMAP nucleophilicity was used to produce the new [Os(bpy)(2)(CO)(Br)]OTf and [Os(bpy)(2)(CO)(I)]OTf complexes which have been fully characterized. (C) 2004 Elsevier B.V. All rights reserved.
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osmium complexes; bipyridil ligands; cyclic voltammetry; dimethylaminopyridine; TRANSITION-METAL COMPLEXES; OXIDATIVE-ADDITION; BOND ACTIVATION; CATALYSTS; LIGANDS; CH2CL2; RUTHENIUM(II); OSMIUM(II); MECHANISMS; ANALOGS
C. Garino; R. Gobetto; C. Nervi; L. Salassa
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/44783
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