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Open AccessArticle

Reduction of 2,2′-Bipyridine by Quasi-Linear 3d-Metal(I) Silylamides—A Structural and Spectroscopic Study

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35037 Marburg, Germany; [email protected] (I.M.)
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Inorganics 2019, 7(10), 117; https://doi.org/10.3390/inorganics7100117
Received: 14 August 2019 / Revised: 18 September 2019 / Accepted: 20 September 2019 / Published: 25 September 2019
(This article belongs to the Special Issue First-Row Transition Metal Complexes)
Quasi-linear anionic 3d-metal(I) silylamides are a new and promising class of molecules. Due to their highly negative reduction potential we wanted to test their capability to reduce substrates under coordination of their monoanionic radicaloid form. In a proof of principle study, we present the results of the reaction of metal(I) silylamides of chromium to cobalt with 2,2′-bipyridine (bipy), the redox non-innocence and reducibility of which was already established. In the course of these studies complexes of the type K{18-crown-6}[M(hmds)2(bipy)] (hmds = –N(SiMe3)2) were obtained. These compounds were isolated and thoroughly characterized to confirm the electron transfer onto the bipyridine ligand, which now acts as a radical monoanion. For comparison of the structural changes of the bipyridine ligand, the analogous zinc complexes were also synthesized. Overall our results indicate that anionic metal(I) silylamides are capable of reducing and ligate substrates, even when the electrochemical reduction potential of the latter is by up to 1 V higher. View Full-Text
Keywords: oxidation state +1; 3d-metals; two-coordinate complexes; electron transfer; N-ligands oxidation state +1; 3d-metals; two-coordinate complexes; electron transfer; N-ligands
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MDPI and ACS Style

Müller, I.; Schneider, C.; Pietzonka, C.; Kraus, F.; Werncke, C.G. Reduction of 2,2′-Bipyridine by Quasi-Linear 3d-Metal(I) Silylamides—A Structural and Spectroscopic Study. Inorganics 2019, 7, 117.

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