Chemical and Electrochemical Redox Behavior of 9-Anthrylmethyl-Functionalized 5-Cyclopentadienyl Derivatives of Rhodium(I)
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- 作者：Maurizio Carano ; Francesca Cicogna ; Irene D'Ambra ; Benedetta Gaddi ; Giovanni Ingrosso ; Massimo Marcaccio ; Demis Paolucci ; Francesco Paolucci ; Calogero Pinzino ; and Sergio Roffia
- 刊名：Organometallics
- 出版年：2002
- 出版时间：December 9, 2002
- 年：2002
- 卷：21
- 期：25
- 页码：5583 - 5593
- 全文大小：349K
- 年卷期：v.21,no.25(December 9, 2002)
- ISSN：1520-6041
文摘
The study of the electrochemical behavior (CV) of 9-anthrylmethylcyclopentadienyl(AnCH2C5H4) derivatives of rhodium(I) and iridium(I) of formula [M(
5-AnCH2C5H4)L2] (M= Rh or Ir; L = 2-C2H4, 1-CO, 2-C8H14, PPh3; L2 = 4-C8H12), 1-8, in strictly aproticconditions, allows a satisfactory interpretation of the observed electrode processes and givesinformation about the location of the redox sites along with the thermodynamic characterization of the corresponding redox processes. These data show that the occurrence of anintramolecular charge-transfer process between the photoexcited 9-anthryl group and thecyclopentadienylmetal unit is a possible route for the observed anthracenic fluorescencequenching in the compounds 1-8. Moreover, a study was carried out on the redox behaviorof these complexes under chemical activation. The one-electron oxidation of compounds 1-8by thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals,whose highly resolved X-band EPR spectra were fully interpreted by computer simulationas well as by semiempirical and DFT calculations of spin density distribution.
5-AnCH2C5H4)L2] (M= Rh or Ir; L = 2-C2H4, 1-CO, 2-C8H14, PPh3; L2 = 4-C8H12), 1-8, in strictly aproticconditions, allows a satisfactory interpretation of the observed electrode processes and givesinformation about the location of the redox sites along with the thermodynamic characterization of the corresponding redox processes. These data show that the occurrence of anintramolecular charge-transfer process between the photoexcited 9-anthryl group and thecyclopentadienylmetal unit is a possible route for the observed anthracenic fluorescencequenching in the compounds 1-8. Moreover, a study was carried out on the redox behaviorof these complexes under chemical activation. The one-electron oxidation of compounds 1-8by thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals,whose highly resolved X-band EPR spectra were fully interpreted by computer simulationas well as by semiempirical and DFT calculations of spin density distribution.