Irwin, Mark and Doyle, Laurence R. and Krämer, Tobias and Herchel, Radovan and McGrady, John E. and Goicoechea, Jose M. (2012) A Homologous Series of First-Row Transition-Metal Complexes of 2,2′-Bipyridine and their Ligand Radical Derivatives: Trends in Structure, Magnetism, and Bonding. Inorganic Chemistry, 51 (22). pp. 12301-12312. ISSN 0020-1669

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Abstract

The organometallic first-row transition-metal complexes [M(2,2′-bipy)(mes)2] (M = Cr (1), Mn (2), Co (4), Ni (5); 2,2′-bipy = 2,2′-bipyridine; mes = 2,4,6-Me3C6H2) were reacted with potassium and a suitable alkali-metal sequestering agent to yield salts of the anionic species [M(2,2′-bipy)(mes)2] −. The neutral parent compounds and their corresponding anionic congeners were characterized by single-crystal X-ray diffraction in [Cr(2,2′-bipy)- (mes)2]·1.5C6H6, [Mn(2,2′-bipy)(mes)2], [Co(2,2′-bipy)- (mes)2]·THF, [Ni(2,2′-bipy)(mes)2], [K(dibenzo-18-crown-6)·THF][Cr(2,2′-bipy)(mes)2]·2THF, [K(18-crown-6)][Mn- (2,2′-bipy)(mes)2]·2THF, [K(18-crown-6)][Mn(2,2′-bipy)- (mes)2]·0.67py·0.67tol, [K(2,2,2-crypt)][Co(2,2′-bipy)- (mes)2], and [K(2,2,2-crypt)][Ni(2,2′-bipy)(mes)2]. These species, along with the previously reported neutral and anionic iron complexes [Fe(2,2′-bipy)(mes)2] 0/− (3/3−), form a homologous series of compounds which allow for an in-depth study of the interactions between metals and ligands. Single-crystal X-ray diffraction data, DFT calculations, and various spectroscopic and magnetic measurements indicate that the anionic complexes (1−−5−) can be best formulated as M(II) complexes of the 2,2′- bipyridyl radical anion. These findings complement recent studies which indicate that bond metric data from single-crystal X-ray diffraction may be employed as an important diagnostic tool in determining the oxidation states of bipyridyl ligands in transition-metal complexes.

Item Type:	Article
Keywords:	Homologous Series; First-Row Transition-Metal Complexes; 2,2′-Bipyridine; Ligand Radical Derivatives; Trends; Structure; Magnetism; Bonding;
Academic Unit:	Faculty of Science and Engineering > Computer Science Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	15512
Identification Number:	https://doi.org/10.1021/ic301587f
Depositing User:	Tobias Kraemer
Date Deposited:	15 Feb 2022 16:25
Journal or Publication Title:	Inorganic Chemistry
Publisher:	American Chemical Society
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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