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Keywords = Ni(II) and Cu(II) complexes of novel bis-chelate oxime-amide ligand

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28 pages, 5753 KB  
Article
Ni(II) and Cu(II) Ion Coordination by the Novel (2E,2′E)-N,N′-(2-Hydroxypropane-1,3-diyl)bis[(2-hydroxyimino)propanamide] Ligand in the Solid State and in Aqueous Medium
by Igor Vasyl Nikolayenko, Carla Bazzicalupi, Thomas-John Theron and Craig Grimmer
Inorganics 2024, 12(12), 330; https://doi.org/10.3390/inorganics12120330 - 17 Dec 2024
Viewed by 1585
Abstract
In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea2poh ligand have been isolated, and their molecular and crystal structures [...] Read more.
In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea2poh ligand have been isolated, and their molecular and crystal structures determined by single crystal X-ray diffraction. Potentiometric titrations were performed on a range of aqueous solutions in both systems, which allowed the identification of various complex species and afforded their stability constants. ESR spectra of samples with optimised concentrations of complexes in Cu(II)–L–H system were recorded. A distinguishing feature of both systems is the dimerization of anionic pseudo-macrocyclic complexes. The latter is caused either by centrosymmetric hydrogen bonding of the hydroxy group on the propane spacer to the oximato oxygen of the opposing unit or by back-to-back π-stacking of planar complex units. ESR measurements indicated likely coupling of Cu-Cu paramagnetic centres in the dimers. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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23 pages, 6719 KB  
Article
Old Acquaintances and Novel Complex Structures for the Ni(II) and Cu(II) Complexes of bis-Chelate Oxime–Amide Ligands
by Carla Bazzicalupi, Craig Grimmer and Igor Vasyl Nikolayenko
Molecules 2024, 29(2), 522; https://doi.org/10.3390/molecules29020522 - 20 Jan 2024
Cited by 3 | Viewed by 2126
Abstract
In the process of systematically studying the methylhydroxyiminoethaneamide bis-chelate ligands with polymethylene spacers of different lengths, L1–L3, and their transition metal complexes, a number of new Ni(II) and Cu(II) species have been isolated, and their molecular and crystal structures were determined using [...] Read more.
In the process of systematically studying the methylhydroxyiminoethaneamide bis-chelate ligands with polymethylene spacers of different lengths, L1–L3, and their transition metal complexes, a number of new Ni(II) and Cu(II) species have been isolated, and their molecular and crystal structures were determined using single-crystal X-ray diffraction. In all of these compounds, the divalent metal is coordinated by the ligand donor atoms in a square-planar arrangement. In addition, a serendipitously discovered new type of neutral Ni(II) complex, where the propane spacer of ligand L2 underwent oxidation to the propene spacer, and one of the amide groups was oxidised to the ketoimine, is also reported. The resulting ligand L2′ affords the formation of neutral planar Ni(II) complexes, which are assembled in the solid state on top of each other, and yield two polymorphic structures. In both structures, the resulting infinite, exclusively parallel metal ion columns in ligand insulation may serve as precursor materials for sub-nano-conducting connectors. Overall, this paper reports the synthesis and characterisation of seven new anionic, cationic, and neutral Ni(II) and Cu(II) complexes, their crystal structures, as well as experimental and computed UV–Vis absorption spectra for two structurally similar Ni(II) complexes, yellow and red. Full article
(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Inorganic Chemistry Section of Molecules 2024)
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