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Main Title: 3d-and 4d-metal(II) complexes of a tris(pyridyl)ethane-derived N-4 ligand – a structural study and reactivity remarks
Author(s): Wiedemann, Dennis
Grohmann, Andreas
Type: Article
Language Code: en
Abstract: A series of complexes of the new N-4 chelate ligand L (L = 1-{6-[1,1-bis(pyridin-2-yl) ethyl] pyridin-2-yl}-N, N-dimethylmethanamine) with intermediate to late divalent transition metal ions M was obtained by the reaction between L and the respective chloride salt or similar precursor in methanol: [MCl2L] (M = Mn, Fe, Co, Ni, Zn; Ru) and [CuClL]Cl. The stereochemical characteristics of the chelate ligand were studied by means of single-crystal X-ray diffraction, and quantified on the basis of several geometric parameters, including the tetragonal distortion Sigma and the continuous symmetry measure S(O-h). The overall distortion of the coordination environment is predomi-nantly determined by the steric demand of the central ion, while electronic or other subtler influences essentially contribute to the distortion of the ligand L. Unlike similar complexes, [(MnCl2L)-Cl-II] cannot be oxidized to a manganese(III) complex by dioxygen, hydrogen peroxide, or iodosylbenzene. In [(RuCl2L)-Cl-II], one chlorido ligand can be exchanged against small p-accepting molecules such as acetonitrile or dinitrogen. L offers an environment ideal for small metal ions (0.4-0.6 angstrom), such as low-spin iron(II), which rationalizes the late onset of thermal spin crossover in the complex [(FeL)-L-II(NCS)(2)].
Issue Date: 2014
Date Available: 13-Sep-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Subject(s): N ligands
coordinative strain
tetradentate ligands
3d-metal complexes
x-ray diffraction
Sponsor/Funder: DFG, SFB 658, Elementarprozesse in molekularen Schaltern auf Oberflächen
Journal Title: Zeitschrift für anorganische und allgemeine Chemie
Publisher: Wiley-VCH
Publisher Place: Weinheim
Volume: 640
Issue: 8-9
Publisher DOI: 10.1002/zaac.201400047
Page Start: 1632
Page End: 1640
EISSN: 1521-3749
ISSN: 0044-2313
Appears in Collections:FG Anorganische Chemie - Festkörper- und Materialchemie » Publications

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