NDLI: Trinuclear nickel and cobalt complexes containing unsymmetrical tripodal tetradentate ligands: syntheses, structural, magnetic, and catalytic properties

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Jeong, Ah Rim Min, Kil Sik Kim, Cheal Lee, Sun Young Shin, Jong Won Hayami, Shinya
Description	Author Affiliation: Shin JW ( Department of Chemistry, Kyungpook National University, Daegu 41566, Republic of Korea.)
Abstract	The coordination chemistries of the tetradentate $N_{2}O_{2}-type$ ligands N-(2-pyridylmethyl)iminodiethanol $(H_{2}pmide)$ and N-(2-pyridylmethyl)iminodiisopropanol $(H_{2}pmidip)$ have been investigated with nickel(II) and cobalt(II/III) ions. Three novel complexes prepared and characterized are $[(Hpmide)_{2}Ni_{3}(CH_{3}COO)_{4}]$ (1), $[(Hpmide)_{2}Co_{3}(CH_{3}COO)_{4}]$ (2), and $[(pmidip)_{2}Co_{3}(CH_{3}COO)_{4}]$ (3). In 1 and 2, two terminal nickel(II)/cobalt(II) units are coordinated to one $Hpmide^{−}$ and two $CH_{3}CO_{2}^{−}.$ The terminal units are each connected to a central nickel(II)/cobalt(II) cation through one oxygen atom of $Hpmide^{−}$ and two oxygen atoms of acetate ions, giving rise to nickel(II) and cobalt(II) trinuclear complexes, respectively. Trinuclear complexes 1 and 2 are isomorphous. In 3, two terminal cobalt(III) units are coordinated to $pmidip^{2−}$ and two $CH_{3}CO_{2}^{−}.$ The terminal units are each linked to a central cobalt(II) cation through two oxygen atoms of $pmidip^{2−}$ and one oxygen atom of a bidentate acetate ion, resulting in a linear trinuclear mixed-valence cobalt complex. 1 shows a weak ferromagnetic interaction with the ethoxo and acetato groups between the nickel(II) ions (g = 2.24, J = 2.35 $cm^{−1}).$ However, 2 indicates a weak antiferromagnetic coupling with the ethoxo and acetato groups between the cobalt(II) ions (g = 2.37, J = −0.5 $cm^{−1}).$ Additionally, 3 behaves as a paramagnetic cobalt(II) monomer, due to the diamagnetic cobalt(III) ions in the terminal units (g = 2.53, \|D\| = 36.0 $cm^{−1}).$ No catalytic activity was observed in 1. However, 2 and 3 showed significant catalytic activities toward various olefins with modest to good yields. 3 was slightly less efficient toward olefin epoxidation reaction than 2. Also 2 was used for terminal olefin oxidation reaction and was oxidised to the corresponding epoxides in moderate yields (34–75%) with conversions ranging from 47–100%. The cobalt complexes 2 and 3 promoted the O–O bond cleavage to ∼75% heterolysis and ∼25% homolysis.
ISSN	14779226
Issue Number	36
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-09-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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