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Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II) and Co(II) Complexes with Iminodiacetamide Ligands

Pantalon Juraj, Natalija; Miletić, Goran I.; Perić, Berislav; Popović, Zora; Smrečki, Neven; Vianello, Robert; Kirin, Srećko (2019) Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II) and Co(II) Complexes with Iminodiacetamide Ligands. Inorganic Chemistry, 58 (24). pp. 16445-16457. ISSN 0020-1669

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Abstract

Metal complexes of iminodiacetamide (imda) ligands and metal ions Zn(II), Cu(II), Ni(II) and Co(II) were prepared, using eight imda ligands (L1-L8) substituted with groups of different steric and electronic properties on the central amine nitrogen atom (hydrogen atom, methyl, isopropyl, benzyl) and the para-position of phenyl rings (nitro, dime-thylamino). The effect of these substituents on the stoichiometry (ML, ML2), geometry and stereochemistry (mer, trans-fac, cis-fac) of the complexes was studied in solid state, in solution and by DFT calculations. X-Ray single crystal and powder diffraction, thermogravimetry, and IR spectroscopy showed that in the solid state imda ligands preferen-tially form trans-fac ML2 complexes, with the exception of the cis-fac complex 7Zn. NMR spectroscopy of diamagnetic Zn(II) and paramagnetic Co(II) complexes revealed the formation of both ML and ML2 complexes in solution, which was also confirmed by UV-Vis titrations. Variable temperature NMR was used to study the effect of the substituent on the central amine nitrogen on the Zn─N bond strength and nitrogen inversion. Relative stabilities of isomers were rationalized by computations and the optimized structures used for the geometry analysis.

Item Type: Article
Uncontrolled Keywords: amines; metals; ligands; crystal structure; molecular structure
Subjects: NATURAL SCIENCES > Chemistry > Inorganic Chemistry
Divisions: Division of Materials Chemistry
Projects:
Project titleProject leaderProject codeProject type
Minimalni umjetni enzimi: Proširenje primjene posredne indukcije na nove supstrate i nove asimetrične reakcije-MArtEnSrećko KirinIP-2014-09-1461HRZZ
Depositing User: Natalija Pantalon Juraj
Date Deposited: 08 Dec 2020 10:25
Last Modified: 08 Dec 2020 10:25
URI: http://fulir.irb.hr/id/eprint/6078
DOI: 10.1021/acs.inorgchem.9b02200

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