• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1200-1204
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• 1999

The reactions of Ru(tpy)Cl3 (tpy = 2,2';6',2"-terpyridine) with new N,N,C-terdentate ligands, 3,2'-annulated-6-(2"-pyridyl)-2-phenylpyridines (1, HL) and the properties of their Ru(II) complexes are described. The distribution ratio of the two possible Ru(II) complexes, a pentaaza-coordinated complex [Ru(tpy)(1-N,N')Cl]+ and a cycloruthenated complex [Ru(tpy)(La-N,N',C)]+ are highly dependent on the length of the polymethylene unit. The trimethylene bridge of the N,N,C-terdentate in pentaaza-coordinated complex is rigid enough to induce an asymmetry in the complex.

• Bulletin of the Korean Chemical Society
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• 제18권11호
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• pp.1183-1185
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• 1997

Dimethylamine complexes of palladium(Ⅱ) [(PCP)Pd(NHMe2)](OTf) (PCP = 2,6-(R2PCH2)2C6H3); R = Ph (1), R = Cy (2)), have been prepared from the reaction of (PCP)Pd(OTf) and dimethylamine. The complex 1 is stable both in solution and in the solid state, while 2 is stable only in solution in the presence of dimethylamine although the formation of 2 in solution is quantitative by NMR Spectroscopy. A solution NMR spectroscopic study shows that dimethylamine favors over carbon monoxide in the coordination sphere of palladium(Ⅱ) having rigid terdentate ligands. The complexes 1 and 2 in chlorinated solvents undergo a chlorine abstract reaction yielding Pd(2,6-(R2PCH2)2C6H3)Cl in the presence of a base such as dimethylamine and DABCO (diazabicyclooctane), in which a transient dimethylamido palladium(Ⅱ) species likely involves.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1614-1616
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• 2005

• Bulletin of the Korean Chemical Society
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• 제18권2호
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• pp.174-179
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• 1997

The synthesis and electronic as well as redox properties of four Ru(Ⅱ) complexes based on the ligand 4'-(4-pyridyl)-3,3';5',3"-bis-dimethylene-2,2';6',2"-terpyridine are reported. Each new complex is of the type [Ru(L)2]n+ and [Ru(tpy)(L)]n+, where L is the terdentate ligand with extra pyridine ring at 4'-position or is a N-methylated ligand and n=2, 3, or 4. Cyclic voltammetry indicates that the first electron added to the complex enters the viologen-type acceptor in N-methylated ligand.

• 대한화학회지
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• 제51권6호
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• pp.499-505
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• 2007

세자리 비스(이미노)알릴 (N,C,N-집게발) 리간드를 가진 단핵 Ni(II) 착물을 발표하고자 한다. 새로운 착물(2,6-(ArN=CH)2C6H3)NiBr (Ar=2,6-dimethylphenyl (1), 2,6-diisopropylphenyl (2))은 산화성 첨가반응에 의해 Ni(COD)2 (COD=1,5-cyclooctadiene)와 1,3-(ArN=CH)2C6H3Br (bis(N-Ar)-2-bromoisophthalaldimine: Ar=Ph-2,6-Me2, Ph-2,6-iPr2) 으로부터 높은 수율로 합성하였다. 리간드와 니켈 착물에 대한 개선된 합성경로에 대하여 설명하고자 한다. 니켈(II) 착물 1, 2는 적외선 분광학, 수소-핵자기공명, 그리고 원소분석에 의해 구조를 밝혔다. 합성한 니켈 착물을 촉매로 사용하여 에틸렌 중합반응을 시도하였으나 목적하는 에틸렌고분자는 얻어지지 않고 소량의 올리고머가 형성되었다. 본 연구에서 합성한 니켈 착물이 에틸렌고분자 촉매반응에 활성을 보이지 않는 이유는 아마도 집게발 착물의 높은 경직성과 리간드의 비치환성 때문에 반응에 필요한 적합한 조건을 제공하지 못 했다고 사료된다.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2471-2476
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• 2007

A series of titanium complexes containing terdentate β-ketoiminate ligands were found to be efficient for the ring-opening polymerization of ε-caprolactone (ε-CL), producing poly(ε-caprolactone) (PCL) with bimodal distribution. Steric factors imposed by methyl substituents on the back bone of the alkoxy group affected significantly the polymerization rate and physical properties of the resulting PCL. Intra- and intermolecular transesterifications rather than disproportional rearrangements were responsible for the bimodal behavior and for the change in the molecular weight (Mw). Dilution with toluene reduced yield, and lowered polydispersity (PDI) and Mw of PCL, while the catalytic activities of the dimeric complex, [Ti(Oi-Pr)2(N-alkoxy-β- ketoiminate)]2 and Ti(Oi-Pr)4 were not sensitive to the added solvent. The dimeric complex showed living character, while other catalysts suffered from chain termination reactions.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.650-654
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• 1992

Absorption and fluorescence spectra are reported for four different 1 : 3 $Dy^{3+}$ : ligand systems in aqueous solution under mild alkaline pH conditions. The ligands included in this study are oxidiacetate, dipicolinate, iminodiacetate and methyliminodiacetate. The oscillator strengths for the 4f→4f multiplet-to-multiplet transitions are empirically determined from the absorption spectra and the intensity parameters ${\Omega}_{\lambda}$}(${\lambda}$ = 2, 4, 6) for the systems are also obtained by applying the Judd-Ofelt theorem to the observed oscillator strengths. The values of the intensity parameters for the systems are compared and discussed in terms of ligand structural properties to investigate how the intensity parameters can response to the minor changes in the ligand environment. In addition, the relative oscillator strengths for fluorescence are evaluated and compared to the results obtained from absorption spectra.

• Bulletin of the Korean Chemical Society
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• 제34권9호
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• pp.2774-2780
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• 2013

Two new isostructural dinuclear complexes, $Ln_2(4-cpa)_6(bpy)_2$ (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenylacetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with $Ln{\cdots}Ln$ separations of 3.967(2) and 3.956(3) ${\AA}$, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.54-59
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• 1992

Spectroscopic measurements and theoretical calculations are performed for the four 1 : 3 Sm(III) : ligand solutions. The ligands included in this study are oxidiacetate, iminodiacetate, methyliminodiacetate and dipicolinate. The oscillator strengths for the $4f{\to}4f$ multiplet-to-multiplet transitions are empirically determined from the absorption spectra. The intensity parameters ${\Omega}_{\lambda}\;({\lambda}=2,\;4,\;6)$ of $Sm^{3+}$(aquo) and ${SmL_3}^{3-}$ complexes are also evaluated by applying the Judd-Ofelt theorem to the observed oscillator strengths. The values of the intensity parameters are compared and discussed in term of structural properties of the complexes. In addition, the fluorescence spectra are reported for the Sm(III) complex systems under mild alkaline condition. The excitation from the $^6H_{5/2}$ ground state to any excited states lying above the emitting energy level $(^4G_{5/2})$ produces four fluorescence bands, following nonradiative transitions from a certain excited state to the $^4G_{5/2}$ state. The ratios of oscillator strengths of ${SmL_3}^{3-}$ complexes to that of $Sm^{3+}$(aquo) are also evaluated from the fluorescence spectra and compared to the results obtained from the absorption bands.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1359-1365
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• 2005

A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.