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• W2089015527 abstract "The title complexes [Mn(X)(CO)3(iPr-DAB)]n (n = 0, X = Br; n = +1, X = donor solvent) undergo a two-electron reduction according to an ECE sequence. The chemical step (C) involves prompt dissociation of the X ligand from the primary one-electron reduction product, followed by instantaneous one-electron reduction of the five-coordinate transient [Mn(CO)3(iPr-DAB)]• producing the anion [Mn(CO)3(iPr-DAB)]-. The latter complex remains rather stable at T < 190 K, whereas at higher temperatures it undergoes an electron-transfer reaction with the parent complexes producing the dimer [Mn(CO)3(iPr-DAB)]2 (the second C step in the overall ECEC sequence). The rate of this reaction decreases in the order THF > MeCN > Br. The driving force for this behavior is the more positive E1/2 value of the redox couple [Mn(CO)3(iPr-DAB)]•/- relative to those of [Mn(Br)(CO)3(iPr-DAB)]0/•- and [Mn(X)(CO)3(iPr-DAB)]+/• (X = donor solvent) and a very short lifetime of the primary reduction products. In contrast, the ligand P(OMe)3 in [Mn{P(OMe)3}(CO)3(iPr-DAB)]• is bound rather firmly at low temperatures, where the ECE sequence to [Mn(CO)3(iPr-DAB)]- via [Mn(CO)3(iPr-DAB)]• is only a minor route. The reduction of [Mn(X)(CO)3(iPr-DAB)] (X = Me, Bz) at room temperature affords the five-coordinate anion [Mn(CO)3(iPr-DAB)]- via dissociation of X• from the one-electron-reduced intermediate [Mn(X)(CO)3(iPr-DAB)]•- detectable by cyclic voltammetry for X = Me. Oxidation of the five-coordinate anion [Mn(CO)3(iPr-DAB)]- produces the dimer [Mn(CO)3(iPr-DAB)]2, following the reverse ECE(C) sequence involved in the reduction path. The direct dimerization of the radicals primarily formed, [Mn(CO)3(iPr-DAB)]•, is probably only a minor alternative route. In the presence of excess P(OMe)3, the principal oxidation product is the cation [Mn{P(OMe)3}(CO)3(iPr-DAB)]+. The five-coordinate anions [Mn(CO)3(α-diimine)]- can be regarded as strongly π-delocalized complexes with the negative charge equally distributed over the α-diimine and CO ligands. The intriguing mechanism of their photochemical formation from fac-[Mn(Br)(CO)3(α-diimine)] at low temperatures has been rectified on the basis of this (spectro)electrochemical study." @default.
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• W2089015527 date "1997-10-01" @default.
• W2089015527 modified "2023-10-03" @default.
• W2089015527 title "Electrochemical and IR/UV−Vis Spectroelectrochemical Studies of <i>fac</i>-[Mn(X)(CO)₃(iPr-DAB)]<i>ⁿ</i> (<i>n</i> = 0, X = Br, Me, Bz; <i>n</i> = +1, X = THF, MeCN, nPrCN, P(OMe)₃; iPr-DAB = 1,4-Diisopropyl-1,4-diaza-1,3-butadiene) at Variable Temperatures: Relation between Electrochemical and Photochemical Generation of [Mn(CO)₃(α-diimine)]^-" @default.
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• W2089015527 doi "https://doi.org/10.1021/om9702791" @default.
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