On the mechanism of formation and spectral properties of radical anions generated by the reduction of –[Re^I(CO)₃(5-nitro-1,10-phenanthroline)]⁺ and –[Re^I(CO)₃(3,4,7,8-tetramethyl-1,10-ph

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• 作者：Larisa L.B. Bracco^a ; Reynaldo O. Lezna^a ; Jackeline Mu&#xf1 ; oz-Zu&#xf1 ; iga^a ; Gustavo T. Ruiz^a ; Mario R. Fé ; liz^a ; Guillermo J. Ferraudi^b ; Fernando S. Garcí ; a Einschlag^a ; ^{fgarciae@quimica.unlp.edu.ar} ; Ezequiel Wolcan^a ; ^{ewolcan@inifta.unlp.edu.ar}
• 关键词：Pulse radiolysis ; Radicals ; Reduction ; Polymers ; Rhenium ; Phenanthroline
• 刊名：Inorganica Chimica Acta
• 出版年：2011
• 出版时间：15 May 2011
• 年：2011
• 卷：370
• 期：1
• 页码：482-491
• 全文大小：637 K

文摘

The electrochemical reduction in aprotic media of –[Re^I(CO)₃L]⁺ pendants in poly-4-vinylpyridine polymers is compared to that of [Re^I(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 [Re^I(CO)₃(NO₂-phen)(CH₃CN)]⁺ and [Re^I(CO)₃(tmphen)(CH₃CN)]⁺, respectively. Similar spectra were obtained for the radical anions -phen and tmphen⁻ after pulse radiolysis experiments with –[Re^I(CO)₃L]⁺-containing polymers. The analysis of the time-resolved difference spectra was performed using “multivariate curve resolution” (MCR) techniques. Unlike , CH₂OH radicals were unable to reduce tmphen ligands. The reaction of and/or CH₂OH with –[Re^I(CO)₃(NO₂-phen)]⁺-containing polymers generates –[Re^I(CO)₃(-phen)] pendants which after disproportionation give rise to products with λ_max = 380 nm. The kinetic behavior of –[Re^I(CO)₃(-phen)] pendants under different experimental conditions is discussed.