Manganese(II) complexes based on sterically hindered {N,O,O} tridentate Schiff bases: synthesis, structures, and properties

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Manganese(II) complexes (DMSO){(DMSO)2bis[5,7-di-tert-butyl-2-(2-hydroxyphenolato)-1,3-benzoxazol-4-ol]}manganese(II) (Ia) and (DMSO)2{bis[5,7-di-tert-butyl-2-(2-hydroxyphenolato)-5-nitro-1,3-benzoxazol-4-ol]}manganese(II) (Ib) are synthesized from the tridentate sterically hindered Schiff bases: condensation products of 4,6-di-tert-butyl-2-aminophenol with salicylaldehyde derivatives N-(3,5-di-tert-butyl-2-oxyphenyl)salicylaldimine and N-(3,5-di-tert-butyl-2-oxyphenyl-5-nitro)salicylaldimine. The structures and compositions of the synthesized metal chelates are characterized by C, H, and N elemental analysis, IR spectroscopy, and magnetochemical measurement data. The EPR data in DMF and toluene are presented for complex Ia. The molecular structures of complexes Ia and Ib are proved by X-ray diffraction (XRD) results (CIF files CCDC nos. 2325776 (Ia) and 2325777 (Ib), respectively). In both complexes, the manganese ion exists in the octahedral {N2O4} ligand environment in which the coordination occurs due to two nitrogen atoms of the benzoxazole cycle and two oxygen atoms of the o-hydroxyphenol group and the apical positions are occupied by the oxygen atoms of two DMSO molecules.

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D. Garnovskii

Southern Scientific Center, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: ayueliseeva@mail.ru
俄罗斯联邦, Rostov-on-Don

V. Vlasenko

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physics

俄罗斯联邦, Rostov-on-Don

K. Lyssenko

Moscow State University

Email: ayueliseeva@mail.ru
俄罗斯联邦, Moscow

P. Knyazev

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physical and Organic Chemistry

俄罗斯联邦, Rostov-on-Don

A. Burlov

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physical and Organic Chemistry

俄罗斯联邦, Rostov-on-Don

Yu. Koshchienko

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physical and Organic Chemistry

俄罗斯联邦, Rostov-on-Don

A. Uraev

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physical and Organic Chemistry

俄罗斯联邦, Rostov-on-Don

S. Levchenkov

Southern Scientific Center, Russian Academy of Sciences

Email: ayueliseeva@mail.ru
俄罗斯联邦, Rostov-on-Don

E. Ivakhnenko

Southern Federal University

Email: ayueliseeva@mail.ru

Research Institute of Physical and Organic Chemistry

俄罗斯联邦, Rostov-on-Don

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2. Scheme 1. Possible reaction pathways of manganese(II) acetate with salicylaldimines H2L and H2L1.

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3. Fig. 1. Experimental (black) and calculated (red) EPR spectra of complex Ia in DMF solution at 295 K (g = 2.00, aMn = 94.4 G).

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4. Scheme 2. Oxidation of the hydroxyl group in complex Ia.

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5. Fig. 2. Changes in the EPR spectra of complex Ia in a toluene solution in the presence of PbO2 at 295 K over time (g = 2.00, aMn = 94.4 Gs); inset – experimental (black) and calculated (red) EPR spectra of the radical of complex Ia (g = 2.00, aH = 1.96 Gs).

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6. Fig. 3. Molecular structure of Ia (thermal ellipsoids with 50% probability).

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7. Fig. 4. Molecular structure of Ib (thermal ellipsoids with 50% probability).

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8. Fig. 5. View (along the c-axis) of a fragment of a one-dimensional chain formed by intermolecular bonds O–H⋯O and C–H⋯O (blue dotted lines) in the crystal structure of Ia.

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9. Fig. 6. View (along the b-axis) of a fragment of a one-dimensional chain formed by intermolecular C–H⋯O bonds (blue dotted lines) in the crystal structure of Ia. Intramolecular O–H⋯O bonds are shown by the green dotted line.

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