Redox potential–structure relationships in metal complexes. Part 3. The electrochemical activation of co-ordinated hydrazido(2–)-ligands

Autor:	Brian A. L. Crichton, Christopher J. Pickett, Jonathan R. Dilworth, Joseph Chatt
Rok vydání:	1981
Předmět:	Ligand Aryl Inorganic chemistry chemistry.chemical_element Protonation General Chemistry Electrochemistry Redox Medicinal chemistry chemistry.chemical_compound Electron transfer chemistry Electrophile Platinum
Zdroj:	J. Chem. Soc., Dalton Trans.. :419-424
ISSN:	1364-5447 0300-9246
DOI:	10.1039/dt9810000419
Popis:	The complexes [Mo(N2RR′)(S2CNMe2)3]+, R,R′= alkyl or aryl, undergo two successive reversible one-electron reductions in non-aqueous electrolytes at platinum or vitreous carbon electrodes. The initial electron-transfer product [Mo(N2RR′)(S2CNMe2)3]0 disproportionates to [Mo(N2RR′)(S2CNMe2)3]+ and to the product of the second electron transfer, [Mo(N2RR′)(S2CNMe2)3]–. Two-electron reduction of the cation leads to electroactivation of the N2RR′ ligand towards attack by electrophiles and reduction/protonation is shown to liberate the free hydrazine, NH2NMe(Ph), in ca. 57% yield. A plausible mechanism for this electroactivation is discussed, and, from studies of related complexes, it is suggested that the redox orbitals of the [Mo(N2R2)(S2CNMe2)3]+ complex are associated with the MoN–N function.
Databáze:	OpenAIRE
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