On the mechanism of formation and spectral properties of radical anions generated by the reduction of ?[ReI(CO)3(5-nitro-1,10-phenanthroline)]+ and ?[ReI(CO)3(3,4,7,8-tetramethyl-1,10-phenanthroline)]+ pendants in poly-4-vinylpyridine polymers

LARISA L.B. BRACCO; R. O. LEZNA; MUÑOZ, JACKELINE; GUSTAVO T. RUIZ; M. R. FELIZ; G. FERRAUDI; FERNANDO S. GARCÍA EINSCHLAG; E. WOLCAN

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Lugar: AMSTERDAM; Año: 2011 vol. 370 p. 482 - 491

0020-1693

Studies in solution and in the solid state of thermal and photochemical reactions of inorganic polymers have been carried out because of their potential application to catalysis and in optical devices. 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 kmax = 380 nm. The kinetic behavior of ?[ReI(CO)3(NO2 ?--phen)] pendants under different experimental conditions is discussed.