• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.559-566
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• 1999

Gas-phase alkylations of delocalized ambident anions, Y---CH---X- where X, Y=CH2, O, or S, have been investigated theoretically at the MP2/6-31+G*//MP2/6-31+G* and QCISD/6-31+G*//MP2/6-31+G* lev-els. O-and S-alkylations (X=O and S) are more favored kinetically by ΔE^≠ = 4.6 and 9.8 kcal mol-1 than the respective C-alkylations even though they are thermodynamically less favored by 22.4 and 6.0 kcal mol-1 respectively. It was found that the transition structures for the C-alkylations are imbalanced due to the endoergic rehybridi-zation of the carbon center from sp2 to sp3 which leads to premature bond contraction of the C-Y bond and delayed bond stretching of the C-X bond. In the O-, or S-alkylation, such endoergic process is not required since the σ-lone pair on O or S is involved in the initial stage of alkylation. The imbalanced TSs for the C-alkylation are accompanied by higher intrinsic barriers and deformation energies.

• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.217-221
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• 1995

Axial coordination of anions or water to the square-planar nickel(Ⅱ) complexes of the hexaaza macrocyclic ligands 1, 2, and 3, which contain two extra uncoordinated tertiary nitrogens, have been investigated in aqueous solutions containing HX (X=Cl-, Br-, NO3-, or ClO4-) and/or NaX. The nickel(Ⅱ) complexes exist in the acidic solutions as equilibrium mixtures of the square-planar [Ni(L)]2+ (L=1, 2, and 3) and octahedral species [Ni(H2L)X2]2+ (H2L=diprotonated form of L). Some octahedral complexes have been isolated and characterized. The solution behaviors of the complexes indicate that the formation of the octahedral complexes are significantly promoted by the protonation of the uncoordinated tertiary amines. The proportion of the octahedral complexes depends on the type of acid, and increases in the order of HBr < HNO3 < HCl.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.273-278
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• 1989

The gas-phase reactions of methyl formate with anions, $-NH_2,\;-OH,\;-CH_2CN$, are studied theoretically using the AM1 method. Stationary points are located by the reaction coordinate method, refined by the gradient norm minimization and characterized by the determination of Hessian matrix. Potential energy profiles and the stationary point structures are presented for all conceivable processes. Four reaction paths are found to be possible: formyl proton and methyl proton abstractions, carbonyl addition, and $S_N2$ process. For the most basic anion $-NH_2$ the proton abstraction path is favored, while in other case, $OH\;and\;-CH_2CN$, the carbonyl addition paths are favored. In all cases the $S_N2$ process is the most exothermic, but due to the relatively high activation barrier the process can be ruled out.

• Bulletin of the Korean Chemical Society
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• 제9권6호
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• pp.362-364
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• 1988

Reaction of Keggin- or Dawson-type heteropolyanions containing two adjacent vanadium atoms with acetic anhydride in the presence of acid produced acylated anions. Heteropolyanions with one or no vanadium atom do not react under the same conditions, indicating that the acyl group is attached to the bridging oxygen atom between the two vanadium atoms. A characteristic infrared band at 1760 $cm^{-1}$ was observed for the acylated anions. The 8-line EPR spectrum shows that one of the vanadium atoms is reduced to V(IV ). The acylated heteropolyanions are easily hydrolyzed, and its acyl group can also be transferred to aniline.

• 한국자기공명학회논문지
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• 제25권4호
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• pp.45-50
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• 2021

A calix[4]pyrrole (1) bearing a quaternary ammonium pendant via its meso phenoxy linker has been synthesized as the bromide salt form. It was revealed by ¹H NMR spectroscopic analyses performed in DMSO-d₆ that receptor 1 binds F^- with high affinity and selectivity over other halide anions. The binding of receptor 1•Br^- with F^- and Cltakes place by anion metathesis with the anions including F^- and Cl^-.

• Environmental Engineering Research
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• 제9권4호
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• pp.184-192
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• 2004

• 대한화학회지
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• 제19권3호
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• pp.207-210
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• 1975

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1202-1204
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• 2014

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.759-762
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• 1993

• Bulletin of the Korean Chemical Society
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• 제15권4호
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• pp.306-310
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• 1994