Reduction–oxidation properties of organotransition-metal complexes. Part 2. The one-electron oxidation of tetracarbonyl(η-cyclopenta-dienyl) vanadium derivatives

Autor: Maureen D. Kitchen, Neil G. Connelly
Rok vydání: 1976
Předmět:
Zdroj: J. Chem. Soc., Dalton Trans.. :2165-2168
ISSN: 1364-5447
0300-9246
DOI: 10.1039/dt9760002165
Popis: Cyclic-voltammetric studies in CH2Cl2 and MeCN have shown that [V(η-C5H5)(CO)3L]{1; L = PPh3, PMePh2, PEt3, P(NMe2)3, P[(OCH2)3CMe], and P(OPh)3} and [V(η-C5H5)(CO)2(dppe)](2; dppe = Ph2PCH2CH3PPh2) are oxidised at a platinum electrode to [V(η-C5H5)(CO)3L]+(3) and [V(η-C5H5)(CO)2(dppe)]+(4) respectively. For L = PPh3,PMePh2,PEt3,and P(NMe2)3, andfor(2), this processis reversible, but for L = P(OPh)3 or P[(OCH2)2-CMe] it is irreversible at all the scan rates used. Complexes (3; L = PPh3 or PMePh2) and (4) may be generated in CH2CL2 by treating (1) or (2) with [p-FC6H4N2][BF4]. and may be isolated, as their [PF6]– salts, by treating (1; L = PPh3) or (2) with [NO][PF6] in mixtures of methanol and toluene. The e.s.r. spectra of the paramagnetic cations are reported.
Databáze: OpenAIRE