Irwin, Mark and Krämer, Tobias and McGrady, John E. and Goicoechea, Jose M. (2011) On the Structural and Electronic Properties of [Zn2(4,4′-bipyridine)(mes)4]n− (n = 0–2), a Homologous Series of Bimetallic Complexes Bridged by Neutral, Anionic, and Dianionic 4,4′-Bipyridine. Inorganic Chemistry, 50 (11). pp. 5006-5014. ISSN 0020-1669

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Abstract

Addition of 1 equiv of potassium metal to a tetrahydrofuran (THF) solution of Zn2(4,4′-bipyridine)(mes)4 (1; mes =2,4,6-Me3C6H2) in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) yielded the radical anionic species [Zn2(4,4′-bipyridine)(mes)4]•–, which was characterized by single crystal X-ray diffraction in [K(18-crown-6)(THF)2][Zn2(4,4′-bipyridine)(mes)4] (2). A similar reaction employing 2 equiv of alkali metal afforded the related complex [K(18-crown-6)]2[Zn2(4,4′-bipyridine)(mes)4] (3). The [Zn2(4,4′-bipyridine)(mes)4]n− (n = 0–2) moieties present in 1–3 are largely isostructural, yet exhibit significant structural variations which arise because of differences in their electronic structure. These species represent a homologous series of complexes in which the ligand exists in three distinct oxidation states. Structural data, spectroscopic measurements, and density functional theory (DFT) calculations are consistent with the assignment of 1, 2, and 3 as complexes of the neutral, radical anionic, and dianionic 4,4′-bipyridyl ligand, respectively. To the best of our knowledge, species 2 and 3 are the first crystallographically characterized transition metal complexes of the 4,4′-bipyridyl radical and dianion.

Item Type:	Article
Keywords:	Structural; Electronic Properties; [Zn2(4,4′-bipyridine)(mes)4]n− (n = 0–2); Homologous Series; Bimetallic Complexes; Bridged; Neutral; Anionic; Dianionic; 4,4′-Bipyridine;
Academic Unit:	Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	15532
Identification Number:	https://doi.org/10.1021/ic200241d
Depositing User:	Tobias Kraemer
Date Deposited:	21 Feb 2022 15:24
Journal or Publication Title:	Inorganic Chemistry
Publisher:	ACS Publications
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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