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; REYNALDO O. LEZNA; JACKELINE MUÑOZ-ZUÑIGA; GUSTAVO T. RUIZ; MARIO R. FÉLIZ; GUILLERMO J. FERRAUDI; FERNANDO S. GARCÍA EINSCHLAG*; EZEQUIEL WOLCAN*

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Año: 2011 vol. 370 p. 482 - 491

0020-1693

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, CH2OH 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.