• 제목/요약/키워드: Electron delocalization

검색결과 44건 처리시간 0.026초

$^{13}C-NMR$ Study of the Applicaton of the “ Tools of Increasing Electron Demand ” to the 8-Aryl-tricyclo $[3.2.1.0^{2,7}]$oct-8-yl Cations

  • Gweon-Young Ryu;Jung-Hyu Shin
    • Bulletin of the Korean Chemical Society
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    • 제12권2호
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    • pp.193-196
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    • 1991
  • The $^{13}C-NMR$ shifts of a series of para-substituted $8-aryl-tricyclo[3.2.1.0^{2,7}]oct-8-yl$ and $9-aryl-tricyclo[3.3.1.0^{2,8}]-non-9-yl$ cations were measured in $FSO_3H/SO_2ClF\ at\-90^{\circ}$ in order to examine whether the ${\rho}^{C^+}$ values can be used as a measure of the geometric influence on the charge delocalization resulting from ${\rho}$ conjugation in rigid tricyclopropylcarbinyl cations. Plot of the ${\Delta}{\delta}^{C+} shifts against the ${\sigma}^{C+}$ constants revealed excellent linear correlation. The 8-aryl tricyclooctyl systems yielded a ${\rho}^{C+}$ value of -5.00 with r = 0.9962. Previous investigation of the 9-aryl-tricyclononyl systems gave a correlation coefficient of r = 0.9948 with a slope of ${\rho}^{C+}$ = -4.95. A fair parallelism exists between the results of $^{19}F-NMR $ studies and the change of ${\rho}^{C+}$ value in these cations. Consequently, it is established that the ${\rho}^{C+}$ value can be used to explain the mechanism of charge stabilization of the rigid cyclopropylcarbinyl cation such as tricyclo $[3.2.1.0^{2,7}]oct-8-yl$ cation.

전이금속(Ⅳ) 착물들의 전자적 성질과 전기 화학적 거동에 관한 연구(Ⅳ) (A Study on the Electronic Properties and Electrochemical Behavior of Transition Metal(Ⅳ) Complexes (Ⅳ))

  • 최칠남;손효열
    • 대한화학회지
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    • 제39권5호
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    • pp.356-363
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    • 1995
  • 유기 리간드(디크로로 비스[η-싸이크로 펜타디엔닐])을 가지고 전이금속 4가$(Nb^{4+}와\;Mo^{4+}$와의 착물들에 대한 거동을 UV-vis 분광학적, 자기적, 그리고 전기화학적 방법에 의해 조사하였다. 2 또는 3개의 에너지 흡수띠가 이들 착물들의 스펙트라에 의해 관찰되었다. 결정장 갈라짐 에너지 크기와 스핀 짝지움 에너지 그리고 결합 세기는 착물들의 스펙트라로부터 얻어졌다. 이들은 비편재화이고, 낮은 스핀 상태이며 그리고 강한 결합 세기임을 알았다. 자기쌍극자 모멘트는 상자기성과 반자기성 착물이었다. 착물들의 산화환원 과정은 비수용매속에서 순환 전압전류법에 의해서 조사되었다. Nb-C 착물의 산화환원 반응과정은 일전자의 확산과 반응 전류에 의한 짝-단일 반응이었고 또한 Mo-C 착물에서는 일전자의 반응전류에 의한 짝-단일 반응이었다.

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반 양성자성 용매속에서 Europium(Ⅲ) 착물에 대한 전자적 성질과 산화 · 환원 반응에 관한 연구 (A Study on the Electronic Properties and Redox Reaction of Europium(Ⅲ) Complexes in Aprotic Solvent)

  • 최칠남;손효열;김세봉
    • 대한화학회지
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    • 제40권1호
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    • pp.65-71
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    • 1996
  • 유기 리간드(tris[3-(trifluoromethylhydroxymethymelene-camphorato])와 tris[3-(heptafluoropropylhydroxymethymelene-camphorato])을 Eu(Ⅲ)와의 착물들에 대한 거동을 UV-vis 분광학적, 자기적, 그리고 전기화학적 방법에 의해 조사하였다. 둘 또는 세개의 에너지 흡수 띠가 이들 착물들의 스펙트라에 의해 관찰되었다. 결정장 갈라짐 에너지 크기와 스핀 짝지움 에너지 그리고 결합 세기는 착물들의 스펙트라로부터 얻어졌다. 이들 착물은 전자 배열이 비 편재화이고, 낮은 스핀 상태이며 그리고 강한 결합 세기임을 알았다. 자기 쌍극자 모멘트는 반 자기성 착물로 나타났다. 착물들의 산화.환원 과정은 반 양성자성 용매속에서 순환 전압 전류법에 의해서 조사하였다. 착물들의 산화.환원 과정은 일전자의 확산전류에 의한 단일-짝 반응이었다.

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Theoretical Studies on the Progonation Equilibria of Benzoyl Derivatives

  • 김왕기;김용빈;김창곤;이본수
    • Bulletin of the Korean Chemical Society
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    • 제22권4호
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    • pp.395-400
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    • 2001
  • The effects of ortho- (R = H and CH3) and Y-substituents (Y = OCH3, CH3H and CN), which are directly attached to the carbonyl carbon, on the protonation equilibria of the para-X-substituted benzoyl derivatives, 4-X -2, 6-di-R-C6H2-C(=O)-Y, are investigated theoretically using the B3LYP method with 6-31+G* basis set. Structurally, both of the (B) and (BH+ ) forms in the species with R = H are nearly coplanar regardless of the Y-substituents implying that the steric repulsion between Y-substituent and R = H is relatively small. In the species with R = CH3 , the tortional angle (Θ) between the carbonyl moiety and aryl ring varies from zero to near right angle depending on the degree of steric repulsion between Y and R = CH3 and the resonance demand. However the reaction energies, ΔG°, for the protonation processes are more favorable for R = CH3 than for R = H due to stronger electron donating effect of R = CH3 , although the species with R = CH3 are unfavorable sterically. On the other hand, the Hammett type plots are progressively better correlated with б+ than with б values on going from Y = OCH3 to Y = CN for both species with R = H and CH3 indicating that the degree of resonance delocalization between carbonyl moiety and X-substituent is increased for a more electron accepting Y-substituent. Nevertheless the effects of R = CH3 on the magnitude of Hammett type reaction constants ( б or б+ ) are not much different from those of R = H.

Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • 대한화학회지
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    • 제55권6호
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    • pp.919-925
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    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

Adsorbed Carbon Formation and Carbon Hydrogenation for CO2 Methanation on the Ni(111) Surface: ASED-MO Study

  • Choe, Sang-Joon;Kang, Hae-Jin;Kim, Su-Jin;Park, Sung-Bae;Park, Dong-Ho;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • 제26권11호
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    • pp.1682-1688
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    • 2005
  • Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.

Synthesis of Dihydroxylated Chalcone Derivatives with Diverse Substitution Patterns and Their Radical Scavenging Ability toward DPPH Free Radicals

  • Kim, Beom-Tae;O, Kwang-Joong;Chun, Jae-Chul;Hwang, Ki-Jun
    • Bulletin of the Korean Chemical Society
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    • 제29권6호
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    • pp.1125-1130
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    • 2008
  • A series of dihydroxylated chalcone derivatives with diverse substitution patterns on a phenyl ring B and the para-substituents on a phenyl ring A were prepared, and their radical scavenging activities were evaluated by simple DPPH test to determine quantitative structure-activity relationship in these series of compounds. The chalcone compounds with the ortho- (i.e. 2',3'- and 3',4'-) and para- (i.e. 2,5'-) substitution patterns show an excellent antioxidant activities (80-90% of control at the concentration of 50 $\mu$M) which are comparable to those of ascorbic acid and $\alpha$ -tocopherol as positive reference materials. On the contrary, the compounds with meta- (i.e. 2',4'-, 3',5'-) substitution pattern demonstrate very dramatic decrease in activities which are around 25% of the control even at the concentration of 200 $\mu$ M (IC50 > 200 $\mu$ M). These dramatic differences could be interpreted in terms of the ease formation of fairly stable semiquinone radicals from the ortho- and parasubstituted chalcone molecules through facilitating electron delocalization. Our results indicate that the substitution patterns of two hydroxyl groups on ring B are very important structural factors for their radical scavenging activity enhancement. Meanwhile, the substituents at para-position of the phenyl ring A of chalcones have no influence on the activity.

Conformational Analysis and Electronic Properties of 2-Cyano-3-(thiophen-2-yl)acrylic Acid in Sensitizers for Dye-sensitized Solar Cells: A Theoretical Study

  • Balanay, Mannix P.;Kim, Se-Mi;Lee, Mi-Jung;Lee, Sang-Hee;Kim, Dong-Hee
    • Bulletin of the Korean Chemical Society
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    • 제30권9호
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    • pp.2077-2082
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    • 2009
  • The conformational and electronic properties of 2-cyano-3-(thiophen-2-yl)acrylic acid (TCA) in analogues used as sensitizers in dye-sensitized solar cells was examined using density functional theory (DFT) and natural bond orbital analysis methods. A relaxed potential energy surface scan was performed on NKX-2677 by rotating the C-C bond between the thiophene and cyanoacrylic acid which yielded activation energy barriers of about 13 kcal/mol for both E and Z configurations. The most stable conformation of all the analogues was E-180 except for NKX-2587 which has an electrostatic repulsion between the oxygen of the coumarin and the nitrogen of the cyanoacrylic acid. The increase in the electron delocalization between the thiophene and cyanoacrylic acid influences the stability for most of the analogues. But for NKX-2600, even though there was a greater deviation from the planarity of TCA, the stability was mainly due to the presence of a weak hydrogen bond between the hydrogen of the methyl group of the amine located in the donor moiety and the nitrogen of the cyanoacrylic acid. The vertical excitation energies of the analogues containing TCA were calculated by time-dependent DFT method. There were slight differences in its vertical excitation energies but the oscillator strengths vary significantly especially in the case of NKX-2600.

이온교환체에 의한 담배 주류연 중 카보닐 화합물의 선택적 흡착 특성 및 흡착 메카니즘 구명 (Investigation of Adsorption Mechanism and Selective Adsorption of Carbonyl Compounds of Mainstream Tobacco Smoke by Ion Exchangers)

  • 이존태;김효근;지상운;황건중;이문수;박진원
    • 한국연초학회지
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    • 제26권2호
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    • pp.159-167
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    • 2004
  • This work has been conducted to select appropriate filter materials for removing carbonyl compounds in mainstream tobacco smoke. To investigate of the usability of this filter materials, two types of bead ion exchangers were synthesized and their adsorption characteristics for carbonyl compounds were investigated. Sulfonic acid group-containing cation exchanger and ammonium group-containing anion exchanger were synthesized by the suspension polymerization of glycidylmethacrylate(GMA) and divinylbenzene(DVB) followed by the subsequent functionalization, respectively. The removal efficiency of carbonyl compounds by these two ion exchangers increased in the presence of moisture. However, the amount of carbonyl compounds adsorbed on the anion exchanger was larger than that on the cation exchanger under two levels of water contents tested. This phenomenon seems to arise from the electron delocalization in carbonyl group of the anion exchangers. There was not any significant relationship between the amount of carbonyl compounds adsorbed on ion exchangers and the length of adsorption column. From the large ion exchange capacity and rapid ion exchange reaction rate of the anion exchanger, it is suggested that the anion exchanger may be a good filter material for removing carbonyl compounds in the mainstream tobacco smoke.

팔면체 [M(Ⅲ)$A_3B_3$] 형태 착물의 쌍극자모멘트에 대한 ${\pi}$ 결합의 영향 [M(Ⅲ) = Ti(Ⅲ), V(Ⅲ), Cr(Ⅲ), Fe(Ⅲ) 및 Ni(Ⅱ) ; A = O 또는 N ; B = N, S 또는 Cl] (The Effect of ${\pi}$ Bonds on the Dipole Moments for Octahedral [M(Ⅲ)$A_3B_3$] Type Complexes [M(Ⅲ) = Ti(Ⅲ), V(Ⅲ), Cr(Ⅲ), Co(Ⅲ) and Ni(Ⅱ) ; A = O or N; B = N, Cl or S])

  • 안상운;박의서;이기학
    • 대한화학회지
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    • 제25권2호
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    • pp.61-66
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    • 1981
  • 팔면체 [M(Ⅲ)$A_3B_3$]형태 착물의 쌍극자모멘트에 ${\pi}$결합 분자궤도함수의 기여분을 계산하는 방법을 발전시켰다. [M(Ⅲ) = Ti(Ⅲ), V(Ⅲ), Cr(Ⅲ), Fe(Ⅲ), 또는 Co(Ⅲ); A = O 또는 N; B = N, S 또는 Cl] 쌍극자모멘트에 대한 ${\pi}$결합 분자궤도함수의 기여분은 ${\sigma}$결합 분자궤도함수의 기여분보다 작지만 비 편재화 ${\pi}$전자를 가지고 있는 킬레이트 착물에 까지도 무시할 수 없음이 발견되었다. 계산한 쌍극자모멘트가 ${\sigma}$결합 형성 만을 가정했을 때 보다 실험치에 가까웠다.

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