• Title/Summary/Keyword: Ni(II) and Pd(II) complexes

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Metal Complexes of Ambidentate Ligand (VIII). Ni (II) and Pd (II) Complexes of Isonitrosomethylacetoacetate Imines (Ambidentate 리간드의 금속착물 (제 8 보). Isonitrosomethylacetoacetate Imine 리간드의 니켈(II) 및 팔라듐(II) 착물)

  • Bon-Chang Goo;Gang-Yeol Choi;Man-Ho Lee;In-Whan Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.662-671
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    • 1993
  • New Ni(II) and Pd(II) complexes of isonitrosomethylacetoacetate imine derivatives, Ni(IMAA-NH)(IMAA-NH'), Ni(IMAA-NH)(IMAA-NR), $Pd(IMAA-NH)_2\;and Pd(IMAA-NR)_2(R=CH_3,\;C_2H_5,\;n-C_3H_7,\;n-C_4H_9,\;or\;CH_2C_6H_5)$, where H-IMAA-NH and H-IMAA-NR represent isonitrosomethylacetoacetate imine and N-alkylisonitrosomethylacetoacetate imine derivative, respectively, have been prepared and the structures of the complexes have been studied by elemental analyses, electronic, infrared, and $^1H-\;and\;^{13}C-NMR$ spectroscopies.

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Synthesis Catalytic Application of Several$d^8Transition Metal Diphosphine Complexes, (MCl_2PP) (M = Ni^{2+}, Pd^{2+}, Pt^{2+}, Au^{3+} ; PP = diphosphines)$ (몇가지 $d^8$ 전이금속-디포스핀 착물 ($MCl_2PP$)의 합성과 촉매적 응용 (M = $Ni^{2+}$, $Pd^{2+}$, $Pt^{2+}$, $Au^{3+}$ ; PP = diphosphines))

  • Park Yu-Chul;Kim Kyung-Chae;Cho Young-Jae
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.685-691
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    • 1992
  • The $d^8$-transition metal complexes containing diphosphine, $MCl_2PP$ were prepared by using $K_nMCl_m$ as starting materials, wherein M were Ni(II), Pd(II), Pt(II) and Au(III) and PP were bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) and bis(diphenylphosphino)ethylene(dppety). The complexes were characterized by the spectral property $(^H-NMR$, $^{31}P-NMR$ and UV-Visible spectra) together with elemental analysis. The complexes were tested for the catalytic activity on the formation reactions of 3(2H)-furanone and cyclic carbonate. The only Ni(II)- and Pd(II)-diphosphine complexes displayed a good catalytic effects in the production of 3(2H)-furanone from 2-methyl-3-butyn-2-ol [reaction (1)]. But all the diphosphine complexes as catalyst were almost inactive towards cyclic carbonate production preaction [reaction (2)].

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Calculation of the Dipole Moments for Octahedral $[M(II)Cl_2O_2N_2]$ Square Planar and Tetrahedral $[Pd(Ⅱ)X_2Y_2]$ Type Complexes [M(Ⅱ) = Ni(Ⅱ) or Co(Ⅱ), X = N and Y = O or S] (팔면체 $[M(II)Cl_2O_2N_2]$, 사각형 및 사면체 $[Pd(Ⅱ) X_2Y_2]$형태 착물의 쌍극자모멘트의 계산 [M(Ⅱ) = Ni(Ⅱ) 또는 Co(Ⅱ), X = N 그리고 Y = O 또는 S])

  • Ahn Sangwoon
    • Journal of the Korean Chemical Society
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    • v.23 no.2
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    • pp.59-64
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    • 1979
  • The dipole moments for octahedral $[M(II)Cl_2N_2O_2]$, square planar and tetrahedral $[Pd(II)X_2Y_2]$ type complexes are calculated, using the approximate molecular orbital theory [M(II) = Ni(II) or Co(II), X = N and Y = O or S]. The calculated dipole moments for these complexes are in reasonable agreement with the experimental values. The possible structures for these complexes are investigated on the basis of the calculated dipole moments.

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Synthesis and Characterization of Square Planar Mixed-Ligand Complexes (II) : Electrophilic and Nucleophilic Reaction of M(S-S)(N-N) Type Complexes with Ni(II), Pd(II), and Pt(II) (평면사각형 혼합 리간드 착물의 합성과 그 특성 (제 2 보) : Ni(II), Pd(II) 및 Pt(II)의 M(S-S)(N-N)형 착물의 친전자성 및 친핵성 반응)

  • OH Sang Oh;Chung Duck Young
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.81-86
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    • 1992
  • The electrophilic and nucleophilic reactions of M(S-S,ph)(N-N,H) (M = Ni(II), Pd(II), Pt(II); (S-S,ph) = 1,2-diphenylethylenedithiolate; (N-N,H)=1,10-phenanthroline) complexes have been investigated. Reaction with norbornadiene depended upon the back donating ability of the central metal ion and produced 2,5-dithia-3,4-diphenyl-tricyclo[4,4,1,0]-undeca-3,8-diene. In the reaction with methyl iodide, the effect of cleavage of (N-N,H) ligand affected the yield of methylated $M(S-S,ph)_2$ product. The structure of the thermolysis product, ${\alpha},{\alpha}{\prime}$-bismethylthiostibene $(CH_3S-SCH_3,ph)$ of methylated complexes indicates that the main product of the nucleophilic reaction is $M(CH_3S-SCH_3,ph)(S-S,ph)$. We have synthesized a new mixed-ligand complex M(S-S,CN)(N-N,H)((S-S,CN) = 1,2-dicyanoethylenedithiolate) through the nucleophilic reaction of ligand.

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Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

  • Raj, Joe Gerald Jesu;Pathak, Devendra Deo;Kapoor, Pramesh N.
    • Journal of the Korean Chemical Society
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    • v.57 no.6
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    • pp.726-730
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    • 2013
  • Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong ${\sigma}$-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, $^1HNMR$, $^{31}PNMR$ and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

Steric and Electronic Effects of Tetradentate Nickel(II) and Palladium(II) Complexes toward the Vinyl Polymerization of Norbornene

  • Lee, Dong-Hwan;Lee, Jung-Hwan;Eom, Geun-Hee;Koo, Hyo-Geun;Kim, Cheal;Lee, Ik-Mo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1884-1890
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    • 2011
  • A series of Ni(II) and Pd(II) complexes bearing N4-type tetradentate ligands, [Ni($X^1X^2$-6-$Me_2bpb$) 1] and [Pd($X^1X^2$-6-$Me_2bpb$) 2]; 6-$Me_2bpb$ = N,N'-(o-phenylene)bis(6-methylpyridine-2-carboxamidate), $X^1$ = Cl, H, or $CH_3$, $X^2$ = $NO_2$, Cl, F, H, $CH_3$, or $OCH_3$) were designed, synthesized, and characterized to investigate electronic and steric effects of ligand on the norbornene polymerization catalysts. Using modified methylaluminoxanes as an activator, the complexes exhibited high catalytic activities for the polymerization of norbornene and the nickel complexes exhibited better catalytic activity the palladium complexes. Ni complex 1a with $NO_2$ group on the benzene ring showed the highest catalytic activity of $4.9{\times}10^6$ g of PNBEs/$mol_{Ni}{\cdot}h$ and molecular weight of $15.28{\times}10^5$ g/mol with PDI < 2.30. Complexes with electron-withdrawing groups are more thermally stable (> 100 $^{\circ}C$), and tend to afford higher polymerization productivities than the ones having electron-donating groups. Amorphous polynorbornenes were obtained with good solubility in halogenated aromatic solvents. A vinyl addition mechanism has been proposed for the catalytic polymerization.

Synthesis, Characterization and Biological Activities of 4-(p-Chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide and Its Metal Complexes

  • Hassanien, Mohammad M.;Mortada, Wael I.;Hassan, Ali M.;El-Asmy, Ahmed A.
    • Journal of the Korean Chemical Society
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    • v.56 no.6
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    • pp.679-691
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    • 2012
  • New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

Electronic Structure and Electrochemistry of Complexes Trans-bis(tri-phenyl phosphine) Palladium(II) and Nickel(II) with Ligands $(CH_3COO-,\;Cl-\;and\;CO)$ (리간드 $(CH_3COO-,\;Cl-,\;CO)$와 트란스-비스(트리페닐포스핀) 팔라듐(II) 과 니켈(II) 착물들에 대한 전자적구조와 전기화학적 연구)

  • Choe Chil Nam;Jung Oh Jin;Kim Se Bong
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.44-50
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    • 1992
  • The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

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Catalytic Reactivity of Transition Metal (Pd, Ni) complexes with Aminophosphines; I. Carbon-Carbon coupling reactions (Aminophosphine류가 배위된 전이금속(Pd, Ni) 착물의 촉매반응; I. 탄소-탄소 짝지움 반응)

  • Jung, Maeng-Joon;Lee, Chul-Jae;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.7 no.1
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    • pp.107-113
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    • 2004
  • Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

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Oligomerizations and Polymerizations of Olefins by Various Late Transition Metal Catalysts

  • Bahuleyan Bijal Kottukkal;Lee Kyoung-Ju;Son Gi-Wan;Choi Jae-Ho;Chandran Deepak;Abraham Sinoj;Ha Chang-Sik;Kim Il
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.155-155
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    • 2006
  • The most commercially and academically advanced catalysts of late transition metals are diimine complexes based on Pd(II)/Ni(II) and bis(imino)pyridyl complexes based on Fe(II)/Co(II). It is well known that the former systems yield branched polyethylenes and the latter linear PEs. In this presentation, effect of extremely bulky ligands with electron withdrawing/donating substituents at a remote position from Ni(II) metal center and of using multi-nuclear homo or hetero multi-metal on the ethylene polymerization is to be paged.

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