☆ 4.7 Article

Di- and Tetra-Nuclear Copper(II), Nickel(II), and Cobalt(II) Complexes of Four Bis-Tetradentate Triazole-Based Ligands: Synthesis, Structure, and Magnetic Properties

INORGANIC CHEMISTRY (2012)

期刊

INORGANIC CHEMISTRY

卷 51, 期 9, 页码 5058-5069

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ic202537c

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Chemistry, Inorganic & Nuclear

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University of Otago
MacDiarmid Institute for Advanced Materials and Nanotechnology
University of Bordeaux
CNRS
Region Aquitaine
GIS Advanced Materials in Aquitaine (COMET)

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摘要

Four bis-tetradentate N-4-substituted-3,5-{bis-[bis-N-(2-pyridinemethyl)]aminomethyl}-4H-1,2,4-triazole ligands, L-Tz1-L-Tz4 differing only in the triazole N-4 substituent R (where R is amino, pyrrolyl, phenyl, or 4-tertbutylphenyl, respectively) have been synthesized, characterized, and reacted with M-II(BF4)(2)center dot 6H(2)O (M-II = Cu, Ni or Co) and Co(SCN)(2). Experiments using all 16 possible combinations of metal salt and L-TzR were carried out: 14 pure complexes were obtained, 11 of which are dinuclear, while the other three are tetranuclear. The dinuclear complexes include two copper(II) complexes, [Cu-2(II)(L-Tz2)(H2O)(4)](BF4)(4) (2), [Cu-2(II)(L-Tz4)(BF4)(2)](BF4)(2) (4); two nickel(II) complexes, [Ni-2(II)(L-Tz1)(H2O)(3)(CH3CN)](BF4)(4)center dot 0.5(CH3CN) (5) and [Ni-2(II)(L-Tz4)(H2O)(4)](BF4)(4)center dot H2O (8); and seven cobalt(II) complexes, [Co-2(II)(L-Tz1)(mu-BF4)](BF4)(3)center dot H2O (9), [Co-2(II)(L-Tz2)(mu-BF4)](BF4)(3)center dot 2H(2)O (10), [Co-2(II)(L-Tz3)(H2O)(2)](BF4)(4) (11), [Co-2(II)(L-Tz4)(mu-BF4)](BF4)(3)center dot 3H(2)O (12), [Co-2(II)(L-Tz1)(SCN)(4)]center dot 3H(2)O (13), [Co-2(II)(L-Tz2)(SCN)(4)]center dot 2H(2)O (14), and [Co-2(II)(L-Tz3)(SCN)(4)]center dot H2O (15). The tetranuclear complexes are [Cu-4(II)(L-Tz1)(2)(H2O)(2)(BF4)(2)](BF4)(6) (1), [Cu-4(II)(L-Tz3)(2)(H2O)(2)(mu-F)(2)](BF4)(6)center dot 0.5H(2)O (3), and [Ni-4(II)(L-Tz3)(2)(H2O)(4)(mu-F-2)](BF4)(6)center dot 6.5H(2)O (7). Single crystal X-ray structure determinations revealed different solvent content from that found by microanalysis of the bulk sample after drying under a vacuum and confirmed that 5', 8', 9', 11', 12', and 15' are dinuclear while 1' and 7' are tetranuclear. As expected, magnetic measurements showed that weak antiferromagnetic intracomplex interactions are present in 1, 2, 4, 7, and 8, stabilizing a singlet spin ground state. All seven of the dinuclear cobalt(II) complexes, 9-15, have similar magnetic behavior and remain in the [HSHS] state between 300 and 1.8 K.

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Bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) as new catalytic material

Joanna Drzezdzon, Celina Mokwa, Artur Sikorski, Patrycja Parnicka, Adriana Zaleska-Medynska, Jacek Malinowski, Magdalena Kwiatkowska, Barbara Gawdzik, Dagmara Jacewicz

Summary: Nowadays, there are studies on the design and synthesis of new catalysts for olefin oligomerization and polymerization, with non-toxic metals and high catalytic activities. Transition metal complex compounds, such as Fe(II), Cr(III), and Zr(II), that contain pyridine or quinoline ligands have been found to exhibit moderate catalytic activity in ethylene and propylene polymerizations. In this study, a new cobalt(II) complex compound with bis(5-chloroquinolin-8-olato)-bis(pyridine) ligands was synthesized and tested for its catalytic activity in reactions of 2-chloro-2-propen-1-ol and norbornene oligomerizations. The results showed that the activated bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) catalyst can promote the formation of oligomers in nitrogen atmosphere, at atmospheric pressure, and at room temperature, demonstrating moderate catalytic activity in norbornene oligomerization and low catalytic activity in 2-chloro-2-propen-1-ol oligomerization.

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