Nickel(II) complex with 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane‡

Mikuriya, Masahiro; Hamagawa, Mayu; Tomioka, Natsuki; Fujimori, Rika; Yoshioka, Daisuke; Hori, Shoichi; Kuriyama, Taro; Sakiyama, Hiroshi; Handa, Makoto; Mitsuhashi, Ryoji

doi:10.1515/chempap-2015-0165

Cited by 6 publications

(9 citation statements)

References 13 publications

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“…The former may be assigned to the Cu(II)/Cu(I) couple for the square-pyramidal copper(II) and the latter may be due to the Cu(II)/Cu(I) couple for the octahedral copper(II) center, suggesting the existence of the two species in solution as found in solution spectra. This is in contrast with the case for the nickel(II) complex with taetacn, which shows only one species in solution [24]. The analytical data, infrared spectra, UV-vis-NIR spectra, and temperature dependence of magnetic susceptibilities are consistent with mononuclear structures with octahedral and square-pyramidal geometries for these systems.…”

Section: Methodscontrasting

confidence: 62%

“…It is to be noted that one pendant arm is protonated and does not take part in coordination to the metal atom. This is in contrast with the case for [Ni(taetacn)](ClO 4 ) 2 ·H 2 O, where the metal atom takes an octahedral geometry with three pendant amino groups [24]. The axial Cu1-N1 distance (2.242(5) Å) is considerably longer than those with the basal Cu-N distances (2.012(4) and 2.015(4) Å).…”

Section: Methodsmentioning

confidence: 69%

“…The ligand taetacn was synthesized by a reaction of tacn with N-(p-tosylsulfonyl)aziridine according to the method described in the literature [24]. Other reagents and solvents were obtained from commercial sources and were used without further purifi cation.…”

Section: Methodsmentioning

confidence: 99%

“…However, there are still only few reports on metal complexes with taetacn [21,22]. Therefore, we have been engaged in synthesis of metal complexes with taetacn and found out that a mononuclear nickel(II) complex with octahedral geometry is formed by reactions of taetacn and nickel(II) salt [24]. …”

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confidence: 99%

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Synthesis, Crystal Structure, and Properties of Copper(II) Complexes with 1,4,7-Tris(2-Aminoethyl)-1,4,7-Triazacyclononane

Mikuriya¹,

Hamagawa²,

Tomioka

et al. 2015

ChemJMold

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Abstract. Three kinds of copper(II) complexes with 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (taetacn), [Cu(taetacn)](ClO 4 ) 2 (1), [Cu(Htaetacn)](ClO 4 ) 3 (2), and [Cu(Htaetacn)](BF 4 ) 3 (3) were synthesized and characterized by elemental analyses, IR and UV-Vis spectroscopies. The spectral features are in harmony with an octahedral geometry for 1 and a square-pyramidal coordination for 2 and 3. The crystal structure of 2 was determined by the single-crystal X-ray diffraction method at 293 K. It crystallizes in the orthorhombic space group Pnma with a = 20.605 (3) Keywords: copper(II) complex, magnetic properties, macrocyclic ligand, 1,4,7-triazacyclononane. IntroductionThere have been a considerable interest in coordination chemistry of macrocyclic ligands in the past fi ve decades [1,2]. Small macrocyclic ligand, 1,4,7-triazacyclononane (tacn), is one of the most studied compounds among macrocyclic ligands [3-6] because of the too small size to incorporate metal ion in the triaza-ring, generating mononuclear metal complexes with a sandwich structure [7] and a piano-stool structure [8]. Previously, we reported on metal complexes with cyclam-based octadentate ligand having four 2-aminoethyl groups as pendant arms, 1,4,8,11-tetrakis(2-aminoethyl)-1,4,8,11-tetraazacyclodecane (taec) [9][10][11][12][13][14][15][16]. The taec ligand forms unique dinuclear metal complexes, where the two metal ions are bound by the four pendant groups outside the cyclam ring. Substitution of the 2-aminoethyl pendant groups by other groups such as salicylideneaminoethyl groups also afforded similar dinuclear metal complexes [17][18][19][20]. Concerning these cyclam-based ligands with four pendant groups, the corresponding tacn-based hexadentate ligands with three pendant groups are of interest [21][22][23]. Especially, 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (taetacn), as shown in Figure 1, is interesting for us due to the comparison with the taec ligand. However, there are still only few reports on metal complexes with taetacn [21,22]. Therefore, we have been engaged in synthesis of metal complexes with taetacn and found out that a mononuclear nickel(II) complex with octahedral geometry is formed by reactions of taetacn and nickel(II) salt [24].

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Section: Methodscontrasting

confidence: 62%

Section: Methodsmentioning

confidence: 69%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Synthesis, Crystal Structure, and Properties of Copper(II) Complexes with 1,4,7-Tris(2-Aminoethyl)-1,4,7-Triazacyclononane

Mikuriya¹,

Hamagawa²,

Tomioka

et al. 2015

ChemJMold

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“…The spectrum is typical for an octahedral nickel(II) complex, and the main bands are assigned while assuming an O symmetry: the lowest transition band around 1088 nm can be assigned to 3 A2 → 3 T2, the second lowest band around 630 nm to 3 A2 → 3 T1( 3 F), and the third lowest band around 363 nm to 3 A2 → 3 T1( 3 P) transition. 10 The magnetic moment of 1 is 3.47 μB at 300 K. This value is larger than the spin-only value of octahedral nickel(II) (2.83 μB, S = 1), being typical for octahedral nickel(II) complexes due to the excited 3 T2 state with the orbital angular momentum. 6,7 As shown in Fig.…”

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confidence: 81%

Ferromagnetic Dinuclear Nickel(II) Complex with a Schiff-base Having a Di-μ-phenolato-μ-methanol-bridged Core

Lim¹,

Shin²,

Ryu

et al. 2017

X-ray Structure Analysis Online

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21Among many transition metal complexes, nickel(II) complexes are interesting, because they provide us complicated features, giving paramagnetic properties with blue color in some cases and diamagnetic properties with yellow color in other cases. 1 We previously reported on dinuclear nickel(II) complexes with some organic chelate ligands having strong-donor atoms, such as thiolate-sulfur and amino-nitrogen, which have square-planar nickel(II), resulting in the diamagnetic property of dinuclear complexes. 2 We also obtained the mixed-spin state of nickel(II) complexes with the coexistence of paramagnetic and diamagnetic nickel(II) ions in the same molecule by introducing an additional donor group to the dinuclear systems.3-5 When chelate ligands have weaker donor atoms, such as pyridine-nitrogen, octahedral paramagnetic nickel(II) complexes were formed. 6 The magnetic interaction between paramagnetic nickel(II) ions is antiferromagnetic in most cases. We observed a ferromagnetic interaction in a dinuclear complex of nickel(II) pivalate.7 Such a ferromagnetic behavior is interesting as a potential magnetic material. Recently we synthesized a dinuclear nickel(II) complex having two-μ-phenolato and μ-aqua bridges with N, N′-disalicylidene-2,2′-(ethylenedioxy)bis(ethylamine) (H2dee), [Ni2(dee)2(μ-H2O)]·2C2H5OH (1), from a reaction of nickel(II) salt and H2dee. 8 In this study, we isolated another dinuclear nickel(II) complex and determined the crystal structure of this complex, which shows a dinuclear core with two-phenolatooxygen bridges and a methanol bridge, as shown in Fig. 1. The presence of the neutral methanol molecule as the bridging group is unique, which was deduced from a charge balance consideration. This paper describes the synthesis, crystal structure, temperature dependence of the magnetic susceptibility, and the electronic spectra of [Ni2(dee)2(μ-CH3OH)]·2CH3OH (2).The ligand H2dee was synthesized by a method described in the literature. 8 The complex was prepared by a 1:1 reaction of H2dee and nickel(II) salt in methanol. To a solution of H2dee (36 mg, 0.1 mmol) in 10 cm 3 of methanol was added 24 mg (0.1 mmol) of nickel(II) chloride hexahydrate. The reaction mixture was stirred overnight at room temperature. The resulting clear-green solution was left for several days to give green crystals. The crystals were collected and dried under a vacuum. Yield, 30 mg (33%). Anal. Found: C, 56.24; H, 5.93; N, 6.16%. Calcd for C43H56N4Ni2O11: C, 56.00; H, 6.12; N, 6.07%. Single crystals suitable for the X-ray structure analysis were obtained from the methanol solution, and the crystal structure was determined by the X-ray diffraction method.

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Tris(ethylenediamine)nickel(II) thio-hydroxogermanate monohydrate: Synthesis, crystal structure, 1H NMR, EPR, optical and magnetic properties

Alahmari

Davaasuren

Emwas

et al. 2019

Inorganica Chimica Acta

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Nickel(II) complex with 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane‡

Abstract: A nickel(II) complex, [Ni(taetacn)](ClO

Cited by 6 publications

References 13 publications

Synthesis, Crystal Structure, and Properties of Copper(II) Complexes with 1,4,7-Tris(2-Aminoethyl)-1,4,7-Triazacyclononane

Synthesis, Crystal Structure, and Properties of Copper(II) Complexes with 1,4,7-Tris(2-Aminoethyl)-1,4,7-Triazacyclononane

Ferromagnetic Dinuclear Nickel(II) Complex with a Schiff-base Having a Di-μ-phenolato-μ-methanol-bridged Core

Tris(ethylenediamine)nickel(II) thio-hydroxogermanate monohydrate: Synthesis, crystal structure, 1H NMR, EPR, optical and magnetic properties

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