• Bulletin of the Korean Chemical Society
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• 제15권10호
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• pp.873-881
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• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2960-2964
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• 2011

The efficient asymmetric hydrosilylation of imines in the presence of polymethylhydrosiloxane has been investigated by screening chiral diamine-zinc complexes. A series of chiral diamine ligands were prepared from optically pure 1,2-diphenyl-1,2-ethanediamine and screened for effectiveness. N-Benzylic substituents were required for high enantioselectivity; ligands with bulky groups or extra coordinating groups such as OH and S lowered the catalytic activity. The level of asymmetric induction was usually in >90% ee range for aromatic imine substrates. A linear correlation between the ee of the ligand and that of the product was observed, indicating the presence of a 1:1 ratio of ligand to metal coordination in the active catalytic complex.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1537-1540
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• 2013

• Bulletin of the Korean Chemical Society
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• 제14권4호
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2006년도 추계학술대회 논문집 Vol.19
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• pp.296-297
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• 2006

유기EL의 발광재료로 쓰일 수 있는 이핵 루테늄착체는 $Ru(bpy)_2Cl_2$와 새롭게 디자인한 가교체 (Bis(-2,2'-dipyridyl ketenylidene)-N,N-1,6-diphenylene diamine)의 반응으로부터 합성하였고, FT-IR, $^1H$-NMR, $^{13}C$-NMR, UV-vis, P.L, C.V를 이용하여 착체의 구조분석, 광학적 특성과 전기화학적인 특성을 측정하였다.

• 대한화학회지
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• 제42권5호
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• pp.539-548
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• 1998

여러자리 산소-질소계 리간드들은 시프염기 리간드인 Bis(salicylidene)-ethylendiamine(BSED), Bis(salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylenetriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) 및 Bis(salicylidene)-tetraethylenepentaamine(BSTP)의 이민기를 수소환원장치에서 백금촉매를 이용하여 네자리 리간드인 N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED)과 N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), 다섯자리 N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), 여섯자리 N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT), 일곱자리 N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine(BHTP) 리간드들을 합성하였다. 리간드들의 양성자 해리상수와 전이금속(Ⅱ)과 착물의 안정도상수는 전위차 적정법으로 측정하였다. 리간드별 전이금속(Ⅱ)이온에 대한 착물 안정도상수값$(logK_{ML})$의 크기는 BHED아연(Ⅱ)의 순서로 이 결과는 Irving-Williams 서열과 잘 일치하여 증가하였다.