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• W2317308921 abstract "The purpose of this work was to explore the possibility of using iron(II) hydrides in CO(2) reduction and to compare their reactivity to that of their ruthenium analogues. Fe(bpy)(P(OEt)(3))(3)H(+) and Ru(bpy)(P(OEt)(3))(3)H(+) do not react with CO(2) in acetonitrile, but the one-electron-reduction products of Ru(bpy)(P(OEt)(3))(3)H(+) and Ru(bpy)(2)(P(OEt)(3))H(+) and the two-electron-reduction product of Fe(bpy)(P(OEt)(3))(3)H(+) do. Ru(bpy)(2)(P(OEt)(3))H(+) also reacts slowly with CO(2) to give a formate complex [as reported previously by Albertin et al. (Inorg. Chem. 2004, 43, 1336)] with a second-order rate constant of ∼4 × 10(-3) M(-1) s(-1) in methanol. The structures for the hydride complexes [Fe(bpy)(P(OEt)(3))(3)H](+) and [Ru(bpy)(2)(P(OEt)(3))H](+) and for the (η(5)-Cp)bis- and -tris-PTA complexes (PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane) of iron(II) are reported. These and the CpFe(CO)(bpy)(+) and Fe(II)PNNP compounds have been subjected to electrochemical and UV-vis spectroscopic characterization. Fe(bpy)(P(OEt)(3))(3)H(+) exhibits a quasi-reversible oxidation at +0.42 V vs AgCl/Ag in acetonitrile; Ru(bpy)(P(OEt)(3))(3)H(+) and Ru(bpy)(2)(P(OEt)(3))H(+) are oxidized irreversibly at +0.90 and +0.55 V, respectively, vs AgCl/Ag. The reduction site for Fe(bpy)(P(OEt)(3))(3)H(+) and Fe(bpy)(P(OEt)(3))(3)(CH(3)CN)(2+) appears to be the metal and gives rise to a two-electron process. The bpy-centered reductions are negatively shifted in the ruthenium(II) hydride complexes, compared to the acetonitrile complexes. The results of attempts to prepare other iron(II) hydrides are summarized." @default.
• W2317308921 created "2016-06-24" @default.
• W2317308921 creator A5007974016 @default.
• W2317308921 creator A5023639462 @default.
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• W2317308921 creator A5051071455 @default.
• W2317308921 date "2010-09-21" @default.
• W2317308921 modified "2023-10-05" @default.
• W2317308921 title "Iron(II) and Ruthenium(II) Complexes Containing P, N, and H Ligands: Structure, Spectroscopy, Electrochemistry, and Reactivity" @default.
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• W2317308921 doi "https://doi.org/10.1021/ic101077t" @default.
• W2317308921 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/20857940" @default.
• W2317308921 hasPublicationYear "2010" @default.
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