• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.542-546
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• 1992

New silicon-monosubstituted (${\eta}^4$-2,3,4,5-tetraphenyl-1-silacyclopentadiene)transi tion metal complexes are described. The new (silole-transition metal complex)Fe$(CO)_3$ was obtained from the reaction of silole-tansition metal complex and Fe$(CO)_5$. We have determined the crystal structure of (${\eta}^4$-exo-cyclopentadienyldicarbonyliron-endo-1-meth yl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl)tric arbonyliron by using graphitemonochromated Mo-$K_{\alpha}radiation. The compound was crystallized in the monoclinic space group $P2_1$/c with a = 8.925(1), b = 18.689(3), c = 19.930(3) ${\AA}$, and ${\beta}$ = 102.02$(1)^{\circ}$. The iron moiety CpFe$(CO)_2$ on silicon is in an axal position. The (silole-transition metal complex) Fe$(CO)_3$ was also prepared through the reaction of (${\eta}^4$-1-chloro-2,3,4,5-tetraphenylsilacyclopentadiene) Fe$(CO)_3$ and metal complex nucleophile. The structure configuration was studied by conventional spectroscopy.

• 대한화학회지
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• 제23권4호
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• pp.198-205
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• 1979

금속이온의 $d^2sp^3$ 혼성궤도함수와 리간드의 singIe basis set 궤도함수를 사용하여 팔면체 [M(II)O_3S_3]$형태 착물의 쌍극자모멘트를 계산하는 원자가결합법을 발전시켰다. [M(III)=V(III), Cr(III), Mn(III), Fe(III), Co(III), Ru(III), Rh(III) 및 Os(III)]. 이 새로운 방법에 있어서 금속이온의 valence basis sets와 리간드 궤도함수사이의 혼성계수가 같다고 가정할 필요가 없으며 이것이 근사분자궤도함수법에 의한 팔면체 전이원소 착물의 쌍극자모멘트를 계산하는 방법과 다른점이다. 원자가결합법에서는 근사분자궤도함수법에서 보다도 훨씬 쉽게 팔면체착물의 쌍극자 모멘트를 계산할 수 있으며 계산한 쌍극자 모멘트의 값이 또한 실험치 범위에든다.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Journal of Korean Society for Atmospheric Environment
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• 제14권E호
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• pp.27-40
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• 1998

The solubility characteristics of organic compounds were studied in terms of the extraction efficiency as a function of the polarity of the organic solvent, and the acidity of water in urban aerosol samples collected in University of East Anglia (UEA), Norwich, England. The extraction efficiency of organic compounds were evaluated with respect to the organic carbon, -nitrogen and -hydrogen by means of a wide range of solvent which include polar and nonpolar organic solvents as well as acids and alkaline water. In addition, after being dissolved in aqueous solution, the aqueous chemistry of organic compounds were studied in terms of the organic metal complexes in aerosol, which were studied with oxalic acid, copper, and zinc. The results of this study indicate that solubility characteristics of organic compounds depend on the polarity of the solvents and the acidity of the solvents. In particular, some organic compounds are water soluble, even though they are much smaller than acetone soluble fractions. In the comparison between polar organic solvent extraction and non- polar organic solvent extraction, it can be thought that significant fraction of organic compounds analysed in the aerosol samples, are polar organic compounds because of the higher extraction efficiencies of organic compounds in polar organic solvent extraction than in nonpolar organic solvent extraction. Regarding the study of the oxalic -metal complexes, it can be thought that most oxalic acids are present in the form of oxalic -copper complexes in the aerosols collected at UEA.

• 대한화학회지
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• 제42권4호
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• pp.416-421
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• 1998

귀금속-티아크라운에테르 착물들의 역상 이온쌍 고성능 액체크로마토그래피(RPIP-HPLC)용리 거동에서 이온쌍 시약의 농도와 리간드 종류 효과를 연구하였다. 귀금속 이온 분석의 선택성은 사용한 티아크라운에테르의 고리를 구성하는 원자들의 수가 작을수록 좋았고, 귀금속-티아크라운에테르 착물의 용리 메카니즘은 이동상 중 이온쌍 시약인 도데실술폰산나트륨염(SDS)의 농도가 10 mM 이하일 경우 이온쌍 형성 메카니즘으로, 10 mM 이상일 경우 미쎌 형성 메카니즘으로 설명되었다. 결론적으로 몇 가지 귀금속-티아크라운에테르 착물들을 최적 조건에서 성공적으로 분리하였고, 흑백사진 정착액 중 Ag(Ⅰ) 이온 분리와 정량에 유용함을 증명하였다.

• 대한화학회지
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• 제29권4호
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• pp.372-381
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• 1985

치환 8-퀴놀린올의 옥소몰리브덴(V)착물을 합성하고 착물의 원소분석, 자외선스펙트럼, 전자스펙트럼 및 전도도를 측정하였고 옥소몰리브덴(VI)착물과 함께 질량분석을 행하여 비교 검토하였다. 옥소몰리브덴(V) 착물은 비전해질이고 몰리브덴-산소의 신축진동은 $940cm^{-1}$ 부근에서 강한 흡수띠가 나타나고 결정장전이와 전하이동 전이가 일어났다. 질량분석 결과로 Mo(V, VI)착물에서 몰리브덴과 리간드의 조성이 1:2임을 확인할 수 있었고 옥소몰리브덴(VI)착물에서는 1:1조성의 착물의 질량수가 나타나지만 옥소몰리브덴(V)에서는 일부만 확인되었다.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.636-646
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• 2009

A series of the noble palladium complexes containing $\beta$-ketoiminate ligands with internal bases, [Pd(${\eta}^3$-allyl)($\beta$- ketoiminate)], [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] and [Pd(Me)($\beta$-ketoiminate)], have been successfully prepared. Crystallographically determined structures showed that these complexes are distorted square planar and pendant bases of the $\beta$-ketoiminate ligands fail to coordinate to the metal in the first two classes of complexes while bases do coordinate in the 3rd class complexes. These complexes are active towards norbornene polymerization on activation with $H(OEt_2)_2BAr^'_4$ (Ar' = 3,5-bistrifluoromethylphenyl) and modified methylalumioxane (MMAO). MMAO is more efficient for the activation for polymerization. Generally, the polymerization activity increases with the following order; [Pd(allyl)($\beta$-ketoiminate)] < [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] < [Pd(Me)($\beta$-ketoiminate)].

• 대한화학회지
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• 제57권6호
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• pp.726-730
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• 2013

Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong ${\sigma}$-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, $^1HNMR$, $^{31}PNMR$ and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

• Bulletin of the Korean Chemical Society
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• 제17권2호
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• pp.173-179
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• 1996

A series of tetradentate Schiff base ligands; [1,2-bis(naphthylideneimino)ethane, 1,3-bis(naphthylideneimino)propane, 1,4-bis(naphthylideneimino)butane, and 1,5-bis(naphthylideneimino)pentane] and their Ni(Ⅱ) complexes have been synthesized. The properties of these ligands and their Ni(Ⅱ) complexes have been characterized by elemental analysis, IR, NMR, UV-vis spectra, molar conductance, and thermogravimetric analysis. The mole ratio of Schiff base to Ni(Ⅱ) metal was found to be 1:1. The electrochemical redox process of the ligands and their Ni(Ⅱ) complexes in DMF and DMSO solution containing 0.1 M tetraethyl ammonium perchlorate (TEAP) as a supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry at glassy carbon electrode. The redox process of the ligands was highly irreversible, whereas redox process of Ni(Ⅱ) complexes were observed as one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials of the Ni(Ⅱ) complexes were affected by the chelate ring size of ligands. The diffusion coefficients of Ni(Ⅱ) complexes containing 0.1 M TEAP in DMSO solution were determined to be 5.7-6.9 × 10-6 cm2/sec. Also the exchange rate constants were determined to be 1.8-9.5 × 10-2 cm2/sec. These values were affected by the chelate ring size of ligands.

• 한국토양비료학회지
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• 제28권2호
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• pp.114-122
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• 1995

토양유기물(土壤有機物)에 의한 중금속(重金屬)의 흡착(吸着)현상을 구명(究明)하기 위하여 이탄토(泥炭土)에서 humic acid를 분리정제(分離精製)하여, humid acid-metal complex 생성반응(生成反應)에 대한 mechanism을 조사(調査)하였다. 1. Humic acid-metal complex의 흡광도(吸光度)는 장파장영역(長波長領域)에서 단파장영역(短波長領域)으로 갈수록 Zn-HA > Cd-HA > Cu-HA의 순(順)으로 증가(增加)하였다. 2. Humic acid의 carboxyl group과 phenolic OH group들이 중금속(重金屬) ion들과 반응(反應)하여 complex를 생성(生成)하였으며 그 생성량(生成量)은 Cu > Zn ≧ Cd의 순(順)이었다. 3. Humic acid-medal complex의 안정도(安定度) 상수(常數)는 pH가 증가(增加)함에 따라 增加하였으며 1차(次) 안정도(安定度) 상수(常數)는 Zn>Cd>Cu 순(順)이었고, 2차(次) 안정도(安定度) 상수(常數)는 Cu>Zn>Cd의 순(順)이었으며, 總安定도 常數는 Cu>Zn>Cd의 순(順)이었다. 4. Humlc acid와 중금속(重金屬)ion들 상호(相互) 간(間)의 평균결합수(平均結合數)는 pH가 증가(增加)함에 따라 Cu>Zn>Cd의 順으고 增加하였다. 5. Humic acid에 의한 중금속(重金屬) ion들의 complex생성과정(生成課程)에서 barboxyl group만이 관여(關與)하는 것과 car-boxyl gruup 및 phenolic OH group이 동시(同時)에 관여(關與)하는 두가지 흡착(吸着)mechanlsm을 제안할 수 있었다.