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Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands (CROSBI ID 271435)

Prilog u časopisu | izvorni znanstveni rad | međunarodna recenzija

Pantalon Juraj, Natalija ; Miletić, Goran I. ; Perić, Berislav ; Popović, Zora ; Smrečki, Neven ; Vianello, Robert ; Kirin, Srećko I. Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands // Inorganic chemistry, 58 (2019), 24; 16445-16457. doi: 10.1021/acs.inorgchem.9b02200

Podaci o odgovornosti

Pantalon Juraj, Natalija ; Miletić, Goran I. ; Perić, Berislav ; Popović, Zora ; Smrečki, Neven ; Vianello, Robert ; Kirin, Srećko I.

engleski

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

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 N atom (H atom, methyl, isopropyl, and benzyl) and the para position of the phenyl rings (nitro and dimethylamino). The effect of these substituents on the stoichiometry (ML and ML2), geometry, and stereochemistry (mer, trans-fac, cis-fac) of the complexes was studied in the solid state, in solution, and by density functional theory calculations. Single-crystal and powder X-ray diffraction, thermogravimetry, and IR spectroscopy showed that in the solid state imda ligands preferentially form trans-facML2 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 N atom on the Zn–N bond strength and nitrogen inversion. The relative stabilities of the isomers were rationalized by computations and the optimized structures used for geometry analysis.

Stereochemistry ; UV–vis titrations ; Variable-temperature NMR ; X-ray diffraction ; DFT calculations

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Podaci o izdanju

58 (24)

2019.

16445-16457

objavljeno

0020-1669

1520-510X

10.1021/acs.inorgchem.9b02200

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Kemija

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