• Bulletin of the Korean Chemical Society
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• 제27권8호
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• pp.1140-1144
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• 2006

A macrocyclic ligand, N,N',N'-tribenzyl-2,11,20-triaza[3,3,3](2,6)pyridinophane (BAPP), was used to prepare an iron(II) complex as a nonheme model complex, $[(BAPP)Fe]^{+2}$ (1). X-ray crystallography of a colorless crystal of 1 revealed that BAPP acted as a pentadentate ligand due to geometrical strain for the formation of a six-coordinate iron(II) complex by BAPP. As a result, the iron center revealed a significantly distorted square pyramidal geometry similar to that found in the active site of taurine dioxygenase (tauD). In the reaction of 1 with PhIO, no intermediate was observed in the UV-visible region of spectrometer at low temperatures. Catalytic oxidations of triphenyl phosphine with PhIO at ${-40^{\circ}C}$ revealed that 1 was able to convert triphenyl phosphine to triphenyl phosphine oxide.23; SSOCHKThioanisole was also oxidized to the corresponding methylphenyl sulfoxide under the same conditions.

• 대한화학회지
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• 제23권6호
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• pp.417-419
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• 1979

• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.211-214
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• 1995

The catalytic activities of palladium(0,Ⅰ,Ⅱ)-diphosphine complexes were investigated in styrene oxidation using H2O2 as terminal oxidant. The rates showed a dependence on the chelate ring patterns of complexes (PdCl2L); 5-membered ring (L=dppe: 1,2-bis(diphenylphosphino)ethane) < 6-membered ring (L=dppp: 1,3-bis(diphenylphosphino)propane) < 4-membered ring (L= dppm: bis(diphenylphosphino)methane). This sequence correlates with the ligand field strength and interactions between metal and phosphine ligands. Pd(Ⅱ,Ⅰ)-diphosphine complexes which are capable of making 4-membered chelate ring showed an enhancement of catalytic activities for styrene oxidation. The catalytic activities of Pd(0,Ⅰ,Ⅱ)-diphosphine complexes are described in terms of electronic and steric factors.

• 한국분말재료학회지
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• 제30권1호
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• pp.53-64
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• 2023

Atomic layer etching (ALE) is a promising technique with atomic-level thickness controllability and high selectivity based on self-limiting surface reactions. ALE is performed by sequential exposure of the film surface to reactants, which results in surface modification and release of volatile species. Among the various ALE methods, thermal ALE involves a thermally activated reaction by employing gas species to release the modified surface without using energetic species, such as accelerated ions and neutral beams. In this study, the basic principle and surface reaction mechanisms of thermal ALE?processes, including "fluorination-ligand exchange reaction", "conversion-etch reaction", "conversion-fluorination reaction", "oxidation-fluorination reaction", "oxidation-ligand exchange reaction", and "oxidation-conversion-fluorination reaction" are described. In addition, the reported thermal ALE processes for the removal of various oxides, metals, and nitrides are presented.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3173-3179
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• 2010

New complex $[Mn(II)H_{1.5}L]_2[Mn(II)H_3L]_2(ClO_4)_5{\cdot}3H_2O$ (1), where $H_3L$ is tris {2-(4-imidazolyl)methyliminoethyl} amine (imtren), has been prepared by reacting manganese(II) perchlorate hexahydrate with the imtren ligand in methanol. X-ray crystallographic study revealed that the imtren ligand hexadentately binds to Mn(II) ion through the three Schiff-base imine N atoms and three imidazole N atoms with a distorted octahedral geometry, and the apical tertiary amine N atom of the ligand pseudo-coordinates to Mn(II), forming overall a pseudo-seven coordination environment. The hydrogen-bonds between imidazole and imidazolate of $[Mn(II)H_{1.5}L]^{0.5+}$ complex ions are extended to build a 2D puckered network with trigonal voids. $[Mn(II)H_3L]^{2+}$ complex ions constitutes another extended 2D puckered layer without hydrogen bonds. Two layers are wedged each other to constitute overall stack of the crystal. Peroxidase activity of complex 1 was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of complex 1. Generation of $ABTS^{+{\cdot}}$ was observed by UV-vis and EPR spectroscopies, indicating that the complex 1, a fully-coordinated mononuclear Mn(II) complex with nitrogen-only ligand, has a heme-independent peroxidase activity.

• Bulletin of the Korean Chemical Society
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• 제24권1호
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• pp.60-64
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• 2003

The reactions of $[Pt(dppf)Cl_2]$ with thiophenol (PhSH), 1-propanethiol (n-PrSH), and 1,3-propanedithiol $(HSCH_2CH_2CH_2SH)$ gave the corresponding Pt-dppf-di(thiolato) compounds, $[Pt(dppf)(SPh)_2]\;(1),\;[Pt(dppf)(S-n-Pr)_2]\;(2),\;and [Pt(dppf)(SCH_2CH_2CH_2S)]\;(3)$, respectively. All products are monomeric and 4-coordinate square-planar compounds and were structurally characterized by X-ray diffraction. Electrochemical measurements (cyclovoltammograms) revealed that the oxidation potential of the dppf ligand appears to depend on the type of the group on the thiolato ligand.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.1007-1010
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• 2011

$Ir(dpq/dpqx)_2$(przl-R) complexes were prepared and their electrochemical properties were investigated, where dpq, dpqx and przl-R represent 2,3-diphenylquinoline, 2,3-diphenylquinoxaline and N-phenyl-R-pyrazolonate derivatives, respectively. The iridium complexes containing dpq and dpqx as main ligands were reported to show red phosphorescence, and involvement of a pyrazolonate ancillary ligand in the iridium complexes led to high luminous efficiency for organic light-emitting diodes. In this study, we synthesized red phosphorescent iridium complexes containing a new pyrazolonate ancillary ligand and investigated the HOMOs, LUMOs and resulting electrochemical gaps of $Ir(dpq/dpqx)_2$(przl-R) by cyclic voltammetry. The emission wavelengths of the complexes at 600 - 640 nm were consistent with the gaps of 1.95 - 2.03 eV measured from reduction and oxidation potentials of the complexes.

• 대한화학회지
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• 제29권3호
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• pp.247-251
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• 1985

네자리 리간드인 ethylenediamine-N,N'-di-S-${\alpha}$-propionic acid (eddp)의 디클로로 코발트(III) 착물을 공기산화법에 의하여 합성하였다. eddp리간드는 코발트(III) 이온에 매우 입체선택적으로 배위하여 ${\Delta}$-S-cis 이성체만을 형성함이 관찰되었다. 합성된 착물의 구조는 원소분석, 적외선 분광분석법, 핵자기 공명 및 흡수스펙트럼으로 확인되었으며 특히 착물의 절대배열은 핵자기공명 스펙트럼으로 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제16권10호
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• pp.981-984
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• 1995

New diamineplatinum(Ⅱ) complexes of cyclohexylidenemalonate (chm) ligand, A2Pt(OOC)2C=C(CH2)4CH2 (1, A2=ethylenediamine (en); 2, A2=propylenediamine (pn); 3, A=NH3; 4, A=isopropylamine (ipa)) have been prepared. Their oxidation with H2O2 has led to the corresponding dihydroxoplatinum(Ⅳ) complexes: cis, cis, trans-A2Pt((OOC)2C=C(CH2)4CH2)(OH)2 (5, A2=en; 6, A2=pn; 7, A=NH3; 8, A=ipa). The title complexes have been characterized by means of various spectroscopies and X-ray crystallography. 5 crystallizes in the monoclinic space group P21/a (Z=4) with a=12.098(7) Å, b=9.552(2) Å, c=16.258(4) Å, β=98.03(5)° and V=1860(1) Å3. The structure was refined to R=0.074. The local geometry around platinum atom is approximately octahedral with each hydroxide group in trans position. These platinum complexes are stable in aqueous solution. Pt(Ⅳ) complexes are readily reduced to the corresponding Pt(Ⅱ) complexes by ascorbic acid.

• 대한화학회지
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• 제28권6호
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• pp.384-392
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• 1984

완전히 포화된 거대고리 리간드의 Fe(II) 착화합물 [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$과 ([14]ane$N_4$:1,4,8,11-tetraazacyclotetradecane) 산소분자간의 반응을 아세토니트릴 용액중에서 연구하였다. [Fe([14]aneTEX>$_4)(CH_3CN)_2]^{2+}$는 산소와 쉽게 반응하여 낮은 스핀 Fe(III) 착화합물 [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$을 생성하고 이는 다시 산화성 탈수소 반응에 의해 낮은 스핀 Fe(II) 착화합물 [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$을 형성한다. [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$의 리간드는 불포화도가 매우 높고 이중결합이 컨쥬게이션 되어 있다. 또한 반응의 중간체로서 [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ 및 [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$도 분리되었다. 이 반응과 관련된 Fe(II) 착화합물들은 일산화탄소와 반응하여 [FeL(CH$_3CN)(CO)]^{2+}$ (L = 거대고리 리간드) 형태의 착화합물을 이룬다. [FeL(CH$_3CN)(CO)]^{2+}$의 $v_{CO}$ 값과 [FeL(CH$_3CN_2)^{2+}$의 Fe(II) ${\to}$ Fe(III)의 전기화학적 산화포텐셜 및 산소에 대한 정성적인 안전성은 거대고리 리간드의 불포화도가 높아질수록 증가한다.