Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands

Two new heteroleptic cobalt(II) complexes (3,6-Cat)Co(R-DAD) (where (3,6-Cat)<sup>2−</sup> is a dianion of 3,6-di-<i>tert</i>-butyl-<i>o</i>-benzoquinone, R-DAD is diisopropyl-1,4-diaza-1,3-butadiene (R = <i>i</i>-Pr (<b>1</b>)) or dicycloh...

Full description

Saved in:
Bibliographic Details
Main Authors: Irina V. Ershova, Maxim V. Arsenyev, Ilya A. Yakushev, Alexandr V. Piskunov
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Molbank
Subjects:
Online Access:https://www.mdpi.com/1422-8599/2025/1/M1972
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1850091439415885824
author Irina V. Ershova
Maxim V. Arsenyev
Ilya A. Yakushev
Alexandr V. Piskunov
author_facet Irina V. Ershova
Maxim V. Arsenyev
Ilya A. Yakushev
Alexandr V. Piskunov
author_sort Irina V. Ershova
collection DOAJ
description Two new heteroleptic cobalt(II) complexes (3,6-Cat)Co(R-DAD) (where (3,6-Cat)<sup>2−</sup> is a dianion of 3,6-di-<i>tert</i>-butyl-<i>o</i>-benzoquinone, R-DAD is diisopropyl-1,4-diaza-1,3-butadiene (R = <i>i</i>-Pr (<b>1</b>)) or dicyclohexyl-1,4-diaza-1,3-butadiene (R = <i>c</i>-Hex (<b>2</b>)) have been synthesized and characterized in detail by IR, UV–Vis–NIR spectroscopy, and elemental analysis. The molecular structure of <b>1</b> was determined by X-ray diffraction analysis. Magnetic properties of <b>1</b> and <b>2</b> were measured both in a solid state and in a solution. According to the single-crystal X-ray diffraction analysis, the metal ion in <b>1</b> has a planar coordination environment, but magnetic susceptibility measurements of the microcrystalline samples of <b>1</b> and <b>2</b> indicate the formation of both forms with tetrahedral (<i>d<sup>7</sup></i>, h.s., S<sub>Co</sub> = 3/2) and planar (<i>d<sup>7</sup></i>, l.s., S<sub>Co</sub> = ½) coordination environments of the metal ion. Absorption spectra of crystalline samples of <b>1</b> and <b>2</b> possess intense absorption band in the NIR region. Electrochemical measurements of <b>1</b> and <b>2</b> were also performed.
format Article
id doaj-art-77b057f22cf144b1ae0219905cbc2dd3
institution DOAJ
issn 1422-8599
language English
publishDate 2025-02-01
publisher MDPI AG
record_format Article
series Molbank
spelling doaj-art-77b057f22cf144b1ae0219905cbc2dd32025-08-20T02:42:22ZengMDPI AGMolbank1422-85992025-02-0120251M197210.3390/M1972Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene LigandsIrina V. Ershova0Maxim V. Arsenyev1Ilya A. Yakushev2Alexandr V. Piskunov3G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina Str., 603950 Nizhny Novgorod, RussiaG. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina Str., 603950 Nizhny Novgorod, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Prosp. 31, 119991 Moscow, RussiaG. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina Str., 603950 Nizhny Novgorod, RussiaTwo new heteroleptic cobalt(II) complexes (3,6-Cat)Co(R-DAD) (where (3,6-Cat)<sup>2−</sup> is a dianion of 3,6-di-<i>tert</i>-butyl-<i>o</i>-benzoquinone, R-DAD is diisopropyl-1,4-diaza-1,3-butadiene (R = <i>i</i>-Pr (<b>1</b>)) or dicyclohexyl-1,4-diaza-1,3-butadiene (R = <i>c</i>-Hex (<b>2</b>)) have been synthesized and characterized in detail by IR, UV–Vis–NIR spectroscopy, and elemental analysis. The molecular structure of <b>1</b> was determined by X-ray diffraction analysis. Magnetic properties of <b>1</b> and <b>2</b> were measured both in a solid state and in a solution. According to the single-crystal X-ray diffraction analysis, the metal ion in <b>1</b> has a planar coordination environment, but magnetic susceptibility measurements of the microcrystalline samples of <b>1</b> and <b>2</b> indicate the formation of both forms with tetrahedral (<i>d<sup>7</sup></i>, h.s., S<sub>Co</sub> = 3/2) and planar (<i>d<sup>7</sup></i>, l.s., S<sub>Co</sub> = ½) coordination environments of the metal ion. Absorption spectra of crystalline samples of <b>1</b> and <b>2</b> possess intense absorption band in the NIR region. Electrochemical measurements of <b>1</b> and <b>2</b> were also performed.https://www.mdpi.com/1422-8599/2025/1/M1972cobaltredox-active ligandcatecholate1,4-diaza-1,3-butadienecharge transferX-ray diffraction
spellingShingle Irina V. Ershova
Maxim V. Arsenyev
Ilya A. Yakushev
Alexandr V. Piskunov
Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
Molbank
cobalt
redox-active ligand
catecholate
1,4-diaza-1,3-butadiene
charge transfer
X-ray diffraction
title Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
title_full Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
title_fullStr Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
title_full_unstemmed Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
title_short Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
title_sort heteroleptic cobalt complexes with catecholate and 1 4 diaza 1 3 butadiene ligands
topic cobalt
redox-active ligand
catecholate
1,4-diaza-1,3-butadiene
charge transfer
X-ray diffraction
url https://www.mdpi.com/1422-8599/2025/1/M1972
work_keys_str_mv AT irinavershova heterolepticcobaltcomplexeswithcatecholateand14diaza13butadieneligands
AT maximvarsenyev heterolepticcobaltcomplexeswithcatecholateand14diaza13butadieneligands
AT ilyaayakushev heterolepticcobaltcomplexeswithcatecholateand14diaza13butadieneligands
AT alexandrvpiskunov heterolepticcobaltcomplexeswithcatecholateand14diaza13butadieneligands