INIFTA   05425
INSTITUTO DE INVESTIGACIONES FISICO-QUIMICAS TEORICAS Y APLICADAS
Unidad Ejecutora - UE
capítulos de libros
Título:
On the Mechanism of Formation and Spectral Properties of Radical Anions Generated by the Reduction of -[ReI(CO)3(L)]+ Pendant Chromophores in Poly-4-Vinylpyridine Polymers
Autor/es:
EZEQUIEL WOLCAN
Libro:
Chemistry Research Summaries. Volume 14
Editorial:
NOVA Publishers
Referencias:
Año: 2014; p. 105 - 106
Resumen:
In this chapter we revise the reduction of ReI chromophores attached to polymeric backbones by electrochemical and pulse radiolysis techniques. The electrochemical reduction in aprotic media of -[ReI(CO)3L]+ pendants in poly-4-vinylpyridine polymers is compared to that of [ReI(CO)3L]+ complexes (L= 5-Nitro-1,10-phenanthroline and 3,4,7,8-tetramethyl-1,10-phenanthroline). The UV-vis absorption spectra of the reduced radical anions of 5-Nitro-1,10-phenanthroline (NO2-phen) and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) were obtained by spectro-electrochemistry of [ReI(CO)3(NO2-phen)(CH3CN)]+ and [ReI(CO)3(tmphen)(CH3CN)]+, respectively. Similar spectra were obtained for the radical anions NO2?--phen and tmphen?- after pulse radiolysis experiments with -[ReI(CO)3L]+-containing polymers. The analysis of the time-resolved difference spectra was performed using ?multivariate curve resolution? (MCR) techniques. Unlike e-solv, C?H2OH radicals were unable to reduce tmphen ligands. The reaction of e-solv and/or C?H2OH with -[ReI(CO)3(NO2-phen)]+-containing polymers generates -[ReI(CO)3(NO2?--phen)] pendants which after disproportionation give rise to products with max = 380 nm. The kinetic behavior of -[ReI(CO)3(NO2?--phen)] pendants under different experimental conditions is discussed.