Cyclic Voltammetry of Palladium(II) Complexes with Tridentate Arsine Ligands. Separation of the Two Single-Electron Transfer Steps of the Pd(II) ↔ Pd(0) Interconversion Based on Thermodynamic and Kinetic Discrimination

Autor:	Alison J. Downard, Alan M. Bond, Lyall R. Hanton, Andrew J. Clayton, David A. McMorran
Rok vydání:	1996
Předmět:	Dimer Kinetics Inorganic chemistry chemistry.chemical_element Disproportionation Electrochemistry Inorganic Chemistry chemistry.chemical_compound Arsine chemistry Physical chemistry Physical and Theoretical Chemistry Cyclic voltammetry Acetonitrile Palladium
Zdroj:	Inorganic Chemistry. 35:7684-7690
ISSN:	1520-510X 0020-1669
Popis:	A detailed electrochemical study of the reduction of the five-coordinate complexes [Pd(mtas)2]2+ and [Pd(ptas)2]2+ (mtas = bis(2-(dimethylarsino)phenyl)methylarsine; ptas = bis(2-(dimethylarsino)phenyl)phenylarsine) has been undertaken in acetonitrile and dichloromethane. When cyclic voltammetry is carried out in acetonitrile at room temperature using conventional scan rates, the main voltammetric feature is a single apparently quasireversible two-electron reduction step. A small peak due to reduction of the Pd(I) dimer [Pd2(L3)2]2+ (L3 = mtas, ptas) formed in a follow-up reaction is also observed. At lower temperatures and faster scan rates, splitting of the two-electron reduction and associated oxidation peak occurs, enabling the thermodynamics and kinetics of the individual one-electron steps to be examined. The intermediate monomeric Pd(I) species are thermodynamically unstable with respect to disproportionation, but slow (relative to the experimental time scale) electrode kinetics for the Pd(I/0) cou...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::3ddb69a8f7b8e5634b91bc27b61474f7 https://doi.org/10.1021/ic960642g Zobrazit plný text záznamu