• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4028-4034
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• 2012

Tris(2-phenylphenoxo)aluminum ($(2-PhC_6H_4O)_3Al$) exists as a dimeric form in toluene. When toluene-insoluble anhydrous cobalt acetate is treated with tris(2-phenylphenoxo)aluminum in toluene, the toluene-soluble adduct $(2-PhC_6H_4O)_3Al{\cdot}Co(OAc)_2$ is formed. The 2-phenylphenoxo ligand in the adduct can be replaced with another aryloxo ligand to give (aryloxo)$(2-PhC_6H_4O)_2Al{\cdot}Co(OAc)_2$ (aryloxo = 2-methylphenoxo, 2-isopropylphenoxo, 4-methylphenoxo, 4-isopropylphenoxo, or 4-tert-butylphenoxo). These complexes are active for butadiene polymerization without gel formation when activated with an equivalent amount of $(2-PhC_6H_4O)AlEt_2$ for 2 h. The highest activity, 175 kg/mol-Co (turnover number, 3200) was achieved with $(2-PhC_6H_4O)_3Al{\cdot}Co(OAc)_2$ at $65^{\circ}C$ for 2 h. The microstructure of the polymer chains is mostly trans-1,4-configuration (70-75%) with the remaining being 1,2-vinyl. The cis-1,4-configuration observed by IR is minimal (1-5%). By replacing the 2-phenylpheoxo with a 4-alkylphenoxo ligand, the amount of 1,4-configuration slightly increases, resulting in increase in the endothermic melting signal at $-30{\sim}50^{\circ}C$ in the DSC curve. The molecular weights of the polymers are high ($M_n$: 300000~800000) with a fairly narrow molecular weight distribution ($M_w/M_n$, 2.0-2.7).

• Journal of Photoscience
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• 제7권1호
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• pp.21-26
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• 2000

The photoemission and excitation spectra of cis-[Cr(cyclam)F$_2$]ClO$_4$ (cyclam = 1,4,8,11-tetraazacy-clotetradecane) taken at 77 K are reported. The 298 K mid- and far-infrared spectra are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. The zero-phonon line In the excitation spectrum splits into two components by 169 cm$^{1}$, and the large $^2$E$_{g}$ splitting can be reproduced by the ligand field theory. According to the ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong c-donor character, and fluoride ligand also has strong $\sigma$- and $\pi$-donor properties toward chromium(III) ion.n.

• Bulletin of the Korean Chemical Society
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• 제18권11호
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• pp.1158-1161
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• 1997

The potentiometric methods have been used to determined the protonation constants (logKiH) for the synthesized 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N''-tri(methylacetic acid) [N3O3-tri(methylacetic acid)] and the stability constants (logKML) of the complexes of divalent and trivalent metal ions with the ligand N3O3-tri(methylacetic acid). The protonation constants of N3O3-tri(methylacetic acid) were 9.70 for logK1H, 9.18 for logK2H, 7.27 for logK3H, 3.38 for logK4H, and 2.94 for logK5H. The stability constants for the complexes of divalent metal ions with N3O3-tri(methylacetic acid) were 10.39 for Co2+, 10.68 for Ni2+, 13.45 for Cu2+, and 13.00 for Zn2+. The order of the stability constants for the complexes of the divalent metal ions with N3O3-tri(methylacetic acid) was Co2+ < Ni2+ < Zn2+ < Cu2+. The stability constants for the complexes of trivalent metal ions with N3O3-tri(methylacetic acid) were 16.20 for Ce3+, 16.40 for Eu3+, 16.27 for Gd3+, and 15.80 for Yb3+. The results obtained in this study were compared to those obtained for similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methylacetic acid) and 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N"-triacetic acid, which have been previously reported.

• Bulletin of the Korean Chemical Society
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• 제27권10호
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• pp.1597-1600
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• 2006

The mononuclear iron complex 1, $Fe^{III}$(Hbida)Cl($H_2O$), was synthesized using a tripodal tetradentate ligand, N-(benzimidazol-2-ylmethyl)iminodiacetic acid (H3bida), which has two carboxylate groups, one benzimida- zoyl group, and one tertiary amine where it serves as a tetradentate chelating ligand for the octahedral Fe(III) ion. The four equatorial positions of the octahedral complex are occupied by two monodentate carboxylates, a benzimidazole nitrogen, and an oxygen of a water molecule. One of the axial positions is occupied by an apical nitrogen of the Hbida and the other by a chloride anion. The mononuclear octahedral complex 1 mimics the geometry of the key intermediate structure of the catalytic reaction cycle proposed for the FeSODs, which is a distorted octahedral geometry with three histidyl imidazoles, an aspartyl carboxylate, a superoxide anion, and a water molecule. The redox potential of complex 1, $E_{1/2}$ is -0.11V vs. Ag/AgCl (0.12 V vs. NHE), which is slightly lower than those reported for the most FeSODs. The magnetic susceptibility of complex 1 at room temperature is 5.83 $\mu$B which is close to that of the spin only value, 5.92 $\mu$B of high-spin d5 Fe(III).

• 대한화학회지
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• 제65권3호
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• pp.203-208
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• 2021

As part of our attempt to discover novel active compounds against multi-drug resistant pathogens, we hereby report two new complexes of iron(III) with formulae: [Fe(L₁)₂(H₂O)₂]Cl₃ and [Fe(L₁)₂(L₂)(H₂O)]Cl₂ where L₁ = 1,10-phenanthroline (C₁₂H₈N₂) and L₂ = guanide (C₅H₄N₅O^-). The synthesized complexes were characterized using spectroscopic analysis (ESI-MS, ICP-OES, FT-IR, and UV-Vis), cyclic voltammetry, CHN analysis, gravimetric chloride determination, melting point determination, and conductance measurement. Octahedral geometries are assigned to both complexes. In vitro antibacterial activity was tested on two Gram-positive (Staphylococcus aureus, Streptococcus epidermidis) and two Gram-negative (Escherichia coli and Klebsiella pneumoniae) bacteria using the disc diffusion method. The complexes demonstrated appreciable activity against these pathogens. Interestingly, the [Fe(L₁)₂(L₂)(H₂O)]Cl₂ complex manifested a higher degree of inhibition against the drug-resistant Gram-negative bacteria than the commercially available drug, namely erythromycin.

• 대한화학회지
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• 제45권5호
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• pp.436-441
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• 2001

77K에서 mer-[Cr(dien)(glygly)]$ClO_4$의 방출 및 들뜬 상태 스펙트럼과 실온에서 적외선 및 가시선 스펙트럼을 측정하였다. 스핀-허용 및 스핀-금지에 해당하는 12개의 전자 전이의 성분을 배정하였다. 관측한 전이를 이용하여 Cr(Ⅲ) 착물에 배위된 원자의 결합성을 결정하기 위해서 리간드장 해석을 수행하였다. 이 연구에서 dien과 glygly 리간드의 아민 N 원자는 강한 $\sigma$-주개 특성을 갖는 반면에, glygly의 펩티드 N 원자는 Cr(Ⅲ) 이온에 약한 $\pi$-주개의 성질이 있음을 확인할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제26권1호
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• pp.72-76
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• 2005

Some mononuclear oxovanadium(IV) complexes having the general formula [VOL(bidentate)] (1-4) of which L is tridentate ONS-donor salicylaldehyde S-methyldithiocarbazate (sal-mdtc$^{2-}$) or salicylaldehyde 4- phenylthiosemicarbazate (sal-phtsc$^{2-}$) and bidentate stands for 2,2'-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized. The complexes were characterized by elemental analyses, FAB mass, UV, IR spectroscopy, and cyclic voltammetry. Two of the complexes [VO(sal-mdtc)(bpy)] (1) and [VO(sal-mdtc) (phen)] (2) were crystallographically characterized. The structures revealed that vanadium atom is octahedrally coordinated by the O, N, and S donor atoms of the tridentate ligand, the two N atoms of bidentate ligand, and the oxo atom. The oxygen donor, occupying an apical position has a trans-labilizing effect, resulting in elongation of the V-N bond. The cyclic voltammograms of the complexes exhibited one cathodic response in the range −d1.45 $\sim$ −f1.52 V due to the reduction of V(IV) to V(III).

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.897-906
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• 1998

A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

• Bulletin of the Korean Chemical Society
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• 제30권5호
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• pp.1026-1030
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• 2009

A novel Schiff base ligand (N, O system) 5-methoxy-2-phenyliminomethylphenol ($5-CH_3O-PMP$) was synthesized. Using the synthesized ligand as a fluorescent reagent, a fluorometric method was developed for the quantitative analysis of Al(III) ion. The quantitative analysis of Al(III) ion was performed by making the complex compound between Al(III) ion and $5-CH_3O-PMP$ in ethanol-water solution (85/15, v/v, pH 6.2). The excitation wavelength (${\lambda}em$) of the complex compound was 397 nm while the emmision wavelength (${\lambda}em$) was 498 nm. The quantitative analysis of Al(III) ion was carried out by estimating the fluorescence intensity. The various calibration curves were used for the quantitative analysis in the range of 0.27$\sim$27 ng/mL Al(III) ion concentrations. The detection limit was 0.027 ng/mL. Using the fluorometric method developed in this study, satisfying results were obtained from various samples such as tap water, hot spring water, river water, sea water and waste water, which contained considerable amounts of interfering ions.

• 대한화학회지
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• 제60권6호
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• pp.402-409
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• 2016

3-Mecaptopropionic acid (MPA) 리간드와 하이브리드 타입 리간드($MPA+CdCl_2$)로 각각 부동화(passivation) 된 2.8 nm 크기의 황화납 콜로이드 양자점 박막을 제작하고, 각각을 대기 중, 질소 분위기에서 열처리, 오존 처리 하였을 때 나타나는 두 양자점 박막의 전자 구조와 조성 원소의 변화를 광전자 분광법을 이용하여 연구하였다. 대기에서 열처리는 리간드 종류와 관계없이 황화납 양자점의 가전자대 시작점이 공통적으로 약한 p-도핑 효과가 있음을 직접적으로 확인할 수 있었다. 또한, 오존처리 후 두 황화납 양자점 표면에 공통적으로 $Pb(OH)_2$, $PbSO_x$, PbO를 형성하는 것을 확인하였다. 하지만, 오존에 의해 형성된 산화물 중 PbO 성분은 특별히 하이브리드 타입 리간드로 부동화 된 양자점에서 형성된 양이 MPA 리간드만으로 부동화 된 양자점과 비교했을 때 감소한 것을 확인할 수 있었다. 이것은 PbS(111) 격자면에 있는 과량의 Pb 표면이 $Cl_2$으로 부동화되면서, Pb 양이온과 오존의 반응을 차단함으로써 PbO의 형성을 어렵게 했기 때문으로 추정된다.