Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Nickel(II)‐, Cobalt(II)‐ und Kupfer(II)‐Komplexe eines N, N′‐bis(2‐hydroxybenzyl)‐substituierten vierzehngliedrigen trans‐N2S2‐Makrocyclus

Mattes, R.; Entian, Thomas

doi:10.1002/zaac.200300227

Cited by 3 publications

(3 citation statements)

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“…Each bridging phenoxy oxygen atom is asymmetrically bound, with one Ni−O bond slightly longer [Ni(1)−O(3) = 2.088(6) Å; Ni(2)−O(2) = 2.076(5) Å] than the other [Ni(1)−O(2) = 1.983(5) Å; Ni(2)−O(3) = 1.987(6) Å]; these latter bond lengths are very similar to those found between the nickel and the terminal phenoxy oxygen atoms [Ni(1)−O(1) = 1.998(5) Å; Ni(2)−O(4) = 1.972(6) Å]. Neither of these distances falls outside the range of average Ni−O phenoxy distances observed in other hexacoordinated nickel(II) complexes [1.971(2)−2.102(7) Å]. − …”

Section: Resultsmentioning

confidence: 75%

“…The angles between the nickel atom and the cis donor atoms also differ from 90°, with values in the range 73. [37][38][39][40][41] The bridging water molecule is nearly symmetrically bonded between the two metal atoms [Ni(1)-O(5) ) 2.253-(7) Å; Ni(2)-O(5) ) 2.232(7) Å]. These distances are considerably longer than the other Ni-O distances in the equatorial plane but are within the normal range observed in other similar nickel(II) complexes.…”

Section: Resultsmentioning

confidence: 97%

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Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

et al. 2006

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Cobalt(II), nickel(II), and copper(II) (1, 2, and 3) complexes of the dianionic form of the bis(phenolate) ligand N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H2L) have been synthesized by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the ligand. When copper is used as the anode, the addition of 1,10-phenanthroline to the electrolytic phase gave rise to a different compound [CuL]2.2CH3CN (4). The compounds [CoL]2.2CH3CN (1), [Ni2L2(H2O)].H2O (2), [CuL]2.3H2O (3), and [CuL]2.2CH3CN (4) were characterized by microanalysis, IR, electronic spectroscopy, FAB mass spectrometry, magnetic measurements and by single-crystal X-ray diffraction. The crystal structures show that the complexes have a dinuclear structure. In compounds 1, 3, and 4, two metal ions are coordinated by the two amine nitrogens and the two phenol oxygen atoms of a deprotonated pendant phenol ligand, with one phenolic oxygen atom from ligand acting as a bridge. In compounds 1 and 3, each metal center has a geometry that is closest to trigonal bipyramidal. Magnetic susceptibility data for both compounds show an antiferromagnetic coupling with 2J = -15 cm(-1) for the cobalt(II) complex and a strong antiferromagnetic coupling with 2J = -654 cm(-1) for the copper(II) complex. However, in 4 the geometry around the metal is closer to square pyramidal and the compound shows a lower antiferromagnetic coupling (2J = -90 cm(-1)) than in 3. The nickel atoms in the dimeric compound 2 are hexacoordinate. The NiN2O4 chromophore has a highly distorted octahedral geometry. In this structure, a dianionic ligand binds to one nickel through the two amine nitrogen atoms and the two oxygen atoms and to an adjacent nickel via one of these oxygen atoms. The nickel atoms are linked through a triple oxygen bridge involving two phenolic oxygens, each from a different ligand, and an oxygen atom from a water molecule. The two nickel ions in 2 are ferromagnetically coupled with 2J = 19.8 cm(-1).

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Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 97%

Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

et al. 2006

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“…No X-ray structure of other cobalt complexes with a coordination sphere composed of two phenolate, two thioether and two pyridine donors are available for comparison. However, the structural parameters of complex 2•py could be compared to other cobalt(II) complexes presenting an O2S2N2 coordination sphere, with O = phenolate, alkoxide or carboxylate, S = thioether and N = pyridyl or neutral amine donors[58][59][60]. The ranges of the Co-O [1.952(3)-2.033(2) Å], Co-N [2.134(3)-2.198(3) Å] and Co-S [2.478(2)-2.657(1) Å] bond lengths in these compounds encompass those observed for 2•py (see above).…”

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confidence: 99%

Cobalt complexes of an OSNSO-tetrapodal pentadentate ligand: Synthesis, structures and reactivity

Thevenin

Daran

Poli

et al. 2021

Inorganica Chimica Acta

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The novel pentadentate tetrapodal proligand 2,6-bis [(2-hydroxyphenyl)sulfanylmethyl]pyridine (1•H2) and its cobalt(II) complex [Co(1)] (2) were synthesized and characterized by several analytical (EA, ESI-MS) and spectroscopic methods (NMR or EPR, FT-IR), including X-ray crystallography for 1•H2. Cyclic voltammetry studies showed that 2 undergoes a reversible metal-based oxidation (Co II /Co III ). Complex 2 was designed to be applied to organometallic mediated radical polymerization (OMRP), however it exhibited an extremely poor solubility in non-coordinating solvents and several vinyl monomers (styrene, vinyl acetate and tert-butyl acrylate), which hampers its potential as moderator. Complex 2 has a high affinity towards Lewis bases, such as pyridine, leading to the clean formation of the monopyridine adduct 2•py, as confirmed by X-ray crystallography. In 2•py, ligand 1 is pentacoordinated to the Co II center, with the two thioether-phenolate (S,O) moieties oriented anti to each other, and the only free coordination site of the octahedron is completed by the additional pyridine, trans to the central pyridine linker of 1. The equilibrium between 2 and 2•py could be studied by 1 H NMR. Complex 2 could be cleanly and quantitatively oxidized to its diamagnetic iodo cobalt(III) analog [Co(1)I] (3), by simple reaction with iodine. The latter could then be subjected to a halide abstraction reaction, mediated by K[B(C6F5)], affording the cationic complex [Co(1)][B(C6F5)], 4. Highlights• Cobalt(II) complexes of a bis(thioether)-bis(phenolato)-pyridyl-based OSNSO-ligand.• Neutral (OSNSO)-cobalt(III) iodide and cationic (OSNSO)-cobalt(III) complexes.• XRD, NMR, CV and EPR studies.• Evaluation in radical polymerization.

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Metallkomplexe mit N₂O₂S₂‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N, N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

Mattes

Mühlenbrock

Leeners

et al. 2004

Zeitschrift anorg allge chemie

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Die makrocyclischen Liganden 6, 10‐Bis(2‐hydro‐xyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecin (1) (L1) und 5, 13‐Bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecin (L4) sowie ihre Nickel(II)‐, Cobalt(II)‐ und Kupfer(II)‐Komplexe wurden hergestellt und durch Röntgenstrukturanalysen charakterisiert. In allen Komplexen haben die Metallionen eine oktaedrische N2O2S2‐Koordinationssphäre. Durch Faltung der Liganden um die N···M···S‐Achse bzw. um die N···M···N′‐Achse resultiert eine all‐cis‐Konfiguration für die Komplexe von L1 und eine trans‐N2‐cis‐O2‐cis‐S2‐Konfiguration für die Komplexe von L4. Der Cobalt(II)‐Komplex [CoL1(‐H)CoL1](ClO4)3 (2) ist dimer. Die Verknüpfung erfolgt über eine kurze Wasserstoffbrückenbindung der Länge 2.402(12)Å. Die Kupfer(II)‐Komplexe von L1 und L4 unterscheiden sich im Hinblick auf die Jahn‐Teller‐Verzerrung.

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Metallkomplexe mit N₂O₂S₂‐Koordinationssphäre. Synthese und Charakterisierung der Nickel(II)‐, Cobalt(II)‐ und Kupfer(II)‐Komplexe eines N, N′‐bis(2‐hydroxybenzyl)‐substituierten vierzehngliedrigen trans‐N₂S₂‐Makrocyclus

Cited by 3 publications

References 19 publications

Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

Cobalt complexes of an OSNSO-tetrapodal pentadentate ligand: Synthesis, structures and reactivity

Metallkomplexe mit N₂O₂S₂‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N, N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

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Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Nickel(II)‐, Cobalt(II)‐ und Kupfer(II)‐Komplexe eines N, N′‐bis(2‐hydroxybenzyl)‐substituierten vierzehngliedrigen trans‐N2S2‐Makrocyclus

Cited by 3 publications

References 19 publications

Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes

Cobalt complexes of an OSNSO-tetrapodal pentadentate ligand: Synthesis, structures and reactivity

Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N, N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

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Metallkomplexe mit N₂O₂S₂‐Koordinationssphäre. Synthese und Charakterisierung der Nickel(II)‐, Cobalt(II)‐ und Kupfer(II)‐Komplexe eines N, N′‐bis(2‐hydroxybenzyl)‐substituierten vierzehngliedrigen trans‐N₂S₂‐Makrocyclus

Metallkomplexe mit N₂O₂S₂‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N, N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden