세자리 Schiff Base 리간드의 Cu (II), Ni (II) 및 Zn (II) 착물에 관한 연구 (제1보)

조기형,Chjo Ki Hyung 대한화학회 1974 대한화학회지 Vol.18 No.3

세자리 schiff base 리간드로서 salicylidene imino-o-thiobenzene은 salicylaldehyde와 o-aminothiolbenzene을 Duff reaction 시킴으로써 합성하였으며 이 리간드와 Cu(II), Ni(II), 및 Zn(II) 이온들과의 반응으로서 새로운 착물 Cu(II)$[C_{13}H_9ONS]{\cdot}3H_2O$, 및 Ni(II)$[C_{13}H_9ONS]{\cdot}3H_2O,\;Zn(II)[C_{13}H_9ONS]{\cdot}3H_2O$들을 합성하였다. 이 착물들은 가시부 자외선스펙트럼, 적외선스펙트럼, TGA, DTA 및 원소분석측정에 의하여 리간드와 금속은 1:1 몰비로 착물을 이루며 Cu(II) 착물은 1수화물 4배위 결합착물이고 Ni(II), 및 Zn(II) 착물은 3수화물, 6배위 결합의 착물임을 알아보았다. The tridentate schiff base, salicylidene imino-o-thiolbenzene, has been synthetized from salicylaldehyde and o-amino thiolbenzene by Duff reaction. The schiff base has been reacted with Cu(II), Ni(II), and Zn(II), to form new complexes; Cu(II)$[C_{13}H_9ONS]{\cdot}3H_2O$, Ni(II)$[C_{13}H_9ONS]{\cdot}3H_2O,\;Zn(II)[C_{13}H_9ONS]{\cdot}3H_2O$ It appears that the Cu(II)-complex has tetra-coordinated configuration with the schiff base and one molecule of water, while the Ni(II) and Zn(II)-complexes have hexacoordinated configuration with the schiff base and three molecules of water. The mole ratio of tridentate schiff base ligand to metals was 1:1. These complexes have been identified by infrared spectra, visible spectra, TGA, DTA and elemental analysis.

네자리 Schiff Base 리간드의 Cobalt(II), Nickel(II) 및 Copper(II) 착물의 합성과 DMSO용액에서 전기화학적 성질

조기형,김종순,Ki-Hyung Chjo,Jong-Soon Kim 대한화학회 1987 대한화학회지 Vol.31 No.6

네자리 Schiff base 리간드인 3,4-bis(salicylidene diimine) toluene [o-BSDT $H_2$]를 salicylaldehyde에 3,4-diaminotoluene를 Duff 반응시킴으로써 합성하였으며 이들 리간드와 Ni(II), Co(II) 및 Cu(II)이온들과의 새로운 착물 [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)_2$] 및 [Cu(o-BSDT)]를 합성하였다. 이들 착물에 대한 원소분석, 전자흡수스펙트럼, 적외선 스펙트럼 및 T.G.A. 측정결과에 의하여 Ni(II)와 Co(II) 착물은 리간드대 금속이 1 : 1 몰비의 4배위 착물임을 알았다. 0.1M TEAP-DMSO 용액에서의 폴라로그래피와 순환전압-전류법을 조사한 결과 [Ni(o-BSDT)${\cdot}(H_2O)_2$]는 비가역적인 electron transfer 다음에 빠른 화학적 반응을 하는 EC반응기구를 보이며 [Co(o-BSDT)${\cdot}(H_2O)_2$]는 Co(II) - Co(I)로의 환원과 Co(II) - Co(III)로의 산화가 일어나며, [Cu(o-BSDT)]착물은 Cu(II) - Cu(I)로의 환원이 일어남이 밝혀졌다. The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

비수용매에서 이핵성 네자리 Schiff Base Nickel(II) 및 Copper(II) 착물들의 전기화학적 성질 (제 1 보)

최기형,최용국,서성섭,이송주,Chjo Ki-Hyung,Choi Yong-Kook,Seo Seong-Seob,Lee Song-Ju 대한화학회 1991 대한화학회지 Vol.35 No.1

이핵성 네자리 Schiff base nickel(II) 및 copper(II) 착물로서 [Ni(II)$_2$(SMPD)$_2$(L)$_2$], [Ni(II)$_2$(SPPD)$_2$(L)$_2$], [Cu(II)$_2$(SMPD)$_2$] 및 [Cu(II)2(SPPD)2](L : Py, DMSO, DMF)들을 합성하여 원소분석, IR-spectrum, T.G.A, D.S.C 및 ESR을 측정하여 이핵성임을 확인하였다. 지지전해질로서 0.1M-TEAP을 포함한 비수용매(Py, DMSO 및 DMF)인 10mM-착물용액의 순환전압전류법과 DPP법으로 전기화학적 성질을 측정한 결과 일핵성인 Cu(II)(SOPD) 및 Ni(II)(SOPD)(L)$_2$는 일전자의 확산지배적인 첫단계 환원과정이 0.1M TEAP-Py 용액에서는 비가역적이고, 0.1M TEAP-DMSO 용액에서는 가역 및 준가역적이고 0.1M TEAP-DMF 용액에서는 가역 및 E.C 반응으로 일어나지만, 이핵성 착물들은 일전자의 확산지배적인 환원과정이 두단계 과정으로 다음과 같이 일어남을 알았다. We synthesized the binuclear Tetradentate Schiff base nickel(II) and copper(II) complexes ; [Ni(II)$_2$(SMPO)$_2$(L)$_2$], [Ni(II)$_2$(SPPD)$_2$(L)$_2$] and [Cu(II)$_2$(SMPD)$_2$] and [Cu(II)$_2$(SPPD)$_2$] (where, L : Py, DMSO and DMF). We identified the structure of these complexes by elemental analysis, IR-spectrum, T.G.A, D.S.C and ESR measurements. According to the results of cyclic voltammetry and DPP measurements in aprotic solvent included 0.1M TEAP as supporting electrolyte, we knew that diffusional controlled redox process of one step with one electron was irreversible process in 0.1M TEAP-Py solution. Also it was reversible or quasi reversible process in 0.1M TEAP-DMSO solution and reversible or E.C reaction mechanism in 0.1M TEAP-DMF solution at mononuclear complexes ; [Cu(II)(SOPD)] and [Ni(II)(SOPD)(L)$_2$]. But, we knew that diffusional controlled redox process of two step for one electron of binuclear complexes was as follows. The values of redox potential for dimeric complexes in 0.1M TEAP-L solution (where, L ; Py, DMSO and DMF) with scan rate 100mV/sec.

비수용매에서 이핵성 네자리 Schiff Base Cobalt(II) 착물들의 전기화학적 성질 (제 3 보)

조기형,최용국,서성섭,이송주,Chjo Ki-Hyung,Choi Yong-Kook,Seo Seong-Seob,Lee Song-Ju 대한화학회 1991 대한화학회지 Vol.35 No.4

이핵성 네자리 Schiff base cobalt(II) 착물로서 [Co(II)$_2$(SMPD)$_2$(L)$_2$] 및 [Co(II)$_2$(SPPD)$_2$(L)$_2$](L ; Py, DMSO, 및 DMF)들을 합성하여 원소분석, IR-spectrum 및 T. G. A을 측정하여 이핵성임을 확인하였다. 지지전해질로서 0.1M-TEAP을 포함한 비수용매(Py, DMSO 및 DMF)인 10 mM-착물용액에서 순환전압전류법과 DPP법으로 전기화학적 성질을 측정한 결과 일핵성인 Co(II)(SOPD)(L)$_2$는 일전자의 확산지배적인 두 단계 환원과정이 0.1 M TEAP-Py와 0.1 M TEAP-DMSO 용액에서는 가역 및 준가역적으로 일어나지만, 이핵성인 [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] 착물들은 비수용매에서 일전자의 확산지배적이고, 비가역적 네단계 환원과정이 Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$으로 일어남을 알았다. We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

Electrochemical Reduction of SOCl2 in Various Solvents

Kim, Woo Seong,Chjo, Ki Hyung,Choi, Yong Kook,Na, Kee Su 한국공업화학회 1996 Journal of Industrial and Engineering Chemistry Vol.2 No.1

Electrochemical reduction of thionyl chloride in aprotic solvents has been studied on a platinum disk electrode with cyclic voltammetric and chronoamperometric techniques. Both DMSO and DMF are better solvents than AN for dissolving reduction products, such as sulfur films on the electrode surface. Reduction currents of thionyl chloride increase slowly in solutions containing higher concentrations than about 50 mM in DMF. However, the reduction currents of thionyl chloride increase steadily in AN and DMSO solutions up to about 300 MM, although the rate of increase becomes slower at higher concentrations. Diffusion coefficients for the reduction of thionyl chloride are affected by the fractional concentration of thionyl chloride in aprotic solvent systems. Diffusion coefficients vary slightly in DMF and AN solutions according to the different concentrations of thionyl chloride, whereas they stay relatively constant in DMSO solution.

세자리 Schiff Base 리간드의 몰리브덴 착물에 관하여 (제1보)

조기형,Ki Hyung Chjo 대한화학회 1973 대한화학회지 Vol.17 No.3

세자리 schiff base리간드로서 salicylidene amino-o-hydroxy benzene 은 salicylaldehyde와 o-amino phenol로서 합성하였으며 이 세자리 schiff base 리간드와 Mo(VI), Mo(V), Mo(IV) 및 Mo(III) 의 과산화상태의 몰리브덴 착물들의 반응으로 새로운 착물[Mo O$_2(H_2O)\;(C_{13}H_9O_2N)]$, [MoO Cl(H$_2O)(C_13H_9O_2N)]$, $[Mo(SCN)_2(H_2O)(C_{13}H_9O2_N)]$ 및 $[Mo(H_2O)_2 (C_{13}H_9O_2N)]_2O$들을 얻었다. 이들 착물에서 Mo(VI), Mo(V) 및 Mo(IV)착물들은 리간드와 몰리브덴의 mole비가 1:1인 착물로서 몰리브덴 이온은 6배위 팔면체로서 주어지나 Mo(III) 착물은 Mo-O-Mo의 산소 bridge bond를 갖는 poly nuclear 착물로서 mole비 1:1인 착물로 주어짐을 원소분석치와 자외선흡광도 및 적외선 spectra의 고찰로서 알아보았다. The tridentate schiff base ligand, salicyliden amino-o-hydroxy benzene, has derived from salicylaldehyde and o-amino phenol. This ligand reacts with a series of Mo (VI), Mo (V), Mo (IV), and Mo (III) oxidated states and forms a new complexes; [Mo O$_2(H_2O)\;(C_{13}H_9O_2N)]$, [MoO Cl$(H_2O)\;(C_{13}H_9O_2N)]$, [Mo(SCN)$_2(H_2O)\;(C_{13}H_9O2_N)]$ 및 $[Mo(H_2O)_2\;(C_{13}H_9O_2N)]_2O$. The Mo (VI), Mo(V) and Mo(Ⅳ) ions in these complexes are octahedron, hexa coordinate, and the mole ratio of these ions to the ligand are 1 : 1, but Mo (III) Complex is a Mo-O-Mo oxygen bridge bond and polynuclear, and the mole ratio of Mo (III) to the ligand 1 : 1 above facts are identified from the data of Infrared spectra, visible spectra, and elemental analysis.

네자리 Schiff Base 리간드의 금속착물에 관한 연구

조기형,오상오,김찬호,Chjo Ki Hyung,Oh Sang-Oh,Kim Chan-ho 대한화학회 1974 대한화학회지 Vol.18 No.3

The tetradentate schiff base ligand, N,N'-bis(salicylaldehyde)-m-phenylenediimine has been prepared from salicylaldehyde and m-phenylenediamine by Duff-reaction. The schiff base ligand has been reacted with Cu(II), Ni(II), Co(II), and Zn(II) to form new complexes; Cu(II)$[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Ni(II)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Co(III)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O and Zn(II)2[C_{20}H_{14}O_2N_2]{\cdot}4H_2O$. It seems to be that the Cu(II), Ni(II) and Co(II) complexes have hexacoordinated configuration with the schiff base and two molecules of water, while Zn(II) complex has tetracoordinated configuration with the schiff base and four molecules of water. The mole ratio of tetradentate schiff base ligand to Cu(II), Ni(II) and Co(II) are 1:1 but to Zn(II) is 1:2. These complexes have been identified by visible spectra, infrared spectra, T.G.A. and elemental analysis. 네자리 schiff리간드는 salicylaldehyde와 m-phenylenediamine을 Duff-반응 시킴으로써 N,N-bis(salicylaldehyde)-m-phenylenediimine을 합성하고 이 리간드와 Cu(II), Ni(II), Co(II) 및 Zn(II) 이온들과의 새로운 착물 Cu(II)$[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Co(II)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O$ 및 Zn(II)$[C_{20}H_{14}O_2N_2]{\cdot}4H_2O$들을 합성하였다. 이들 착물에 대하여 가시부 흡수스펙트럼, 적외선스펙트럼, TGA, X-ray 회절 및 원소분석 결과에 의하여 Cu(II), Ni(II) 및 Co(II) 착물들은 리간드와 금속이 1:1 몰비 및 2수화물의 6배위 착물로 주어지며 Zn(II) 착물은 1:2 몰비 4배위 착물로 주어짐을 알았다

세자리 Schiff Base 리간드의 몰리브덴 착물에 관한 연구 (제 2 보)

조기형,Ki Hyung Chjo 대한화학회 1974 대한화학회지 Vol.18 No.1

DMSO용액에서 네자리 Schiff Base Cobalt(II) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 1 보)

조기형,정진순,함희석,서성섭,Chjo Ki-Hyung,Jin-Soon Chung,Heui-Suk Ham,Seoing-Seob Seo 대한화학회 1987 대한화학회지 Vol.31 No.6

네자리 schiff base cobalt(II) 착물로서 Co(SED), Co(SND) and Co(SOPD)들을 합성하여 이들 착물들의 DMSO 용액에서 산소를 가하여 산소첨가 생성착물로 $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ 및 $[Co(SOPD)(DMSO)]_2O_2$들을 합성하였다. 이들의 원소분석과 Cobalt정량, IR-Spectra, T.G.A. 및 자화율을 측정하여 산소:cobalt(II) 착물의 결합비가 1:2이고 네자리 schiff base cobalt(II)와 DMSO 및 산소가 6배위 결합으로 주어짐을 알았으며 Co(SED), Co(SND) 및 Co(SOPD) 착물들의 0.1M TEAP-DMSO용액에서 순환전압-전류법에 의한 산화 환원 과정이 Co(SED) 및 Co(SOPD)는 Co(II) / Co(III)와 Co(II) / Co(I) 과정이 가역적으로 일어나고 Co(SND)는 Co(II) / Co(III)과정은 가역적이지만 Co(II) / Co(I) 과정은 비가역적이다. 또한 산소 첨가 생성물의 착물들은 0.1M TEAP-DMSO 용액에서 산소결합의 환원과정이 $E_{pc}$ = -0.80~-0.89V에서 일어나고 이에 Couple인 산화과정은 $E_{pa}$ = -0.70~-0.76V에서 준가역적으로 일어남을 알았다. Tetradentate schiff base cobalt(II) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(III) complexes; $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ and $[Co(SOPD)(DMSO)]_2O_2$. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (III), DMSO and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(II) / Co(III) and Co(II) / Co(I) for cobalt(SED) and cobalt(SOPD) complexes and Co(II) / Co(III) process for cobalt(SND) complex are reversible process but Co(II) / Co(I) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, $E_{pc}$ = -0.80~-0.89V and $E_{pa}$ = -0.70~-0.76V.

Electrochemical Reduction of Thionyl Chloirde: Solvent Effects

Choi, Yong-Kook,Chjo, Ki-Hyung,Kim, Hyeon-Soo Korean Chemical Society 1994 Bulletin of the Korean Chemical Society Vol.15 No.6