• Title/Summary/Keyword: Palladium complexes

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Palladium(II) Schiff Base Complexes Derived from Allylamine and Vinylaniline

  • Uh, Yoon-Seo;Zhang, Hai-Wen;Vogels, Christopher M.;Decken, Andreae;Westcott, Stephen A.
    • Bulletin of the Korean Chemical Society
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    • v.25 no.7
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    • pp.986-990
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    • 2004
  • Condensation of salicylaldehyde $(2-HOC_6H_4C(O)H)$ with allylamine afforded the unsaturated salicylaldimine, $2-HOC_6H_4C(H)=NCH_2CH=CH_2$. Similar reactivity was observed with substituted salicylaldehydes. Further reaction of these Schiff bases with palladium acetate or $Na_2PdCl_4$ afforded complexes of the type $PdL_2$, where L = deprotonated Schiff base. The molecular structure of the parent salicylaldimine palladium complex $[trans-(2-OC_6H_4C(H)=NCH_2CH=CH_2)_2Pd]$ (1) was characterized by an X-ray diffraction study. Crystals of 1 were monoclinic, space group $P2_1/n,\;a\;=\;14.0005(9)\;{\AA},\;b\;=7.2964(5)\;{\AA},\;c\;=\;17.5103(12)\;{\AA},\;{\beta}\;=\;100.189(1)^{\circ}$, Z = 4. Analogous chemistry with 4-vinylaniline also gave novel palladium complexes containing a pendant styryl group. Crystals of $[trans-(2-HOC_6H_4C(H)=N-4-C_6H_4CH=CH_2)_2Pd]$ (4) were monoclinic, space group $P2_1/c$, a = 13.7710(14) ${\AA}$, b = 11.0348(11) ${\AA}$, c = 7.8192(8) ${\AA}$, ${\beta}\;=\;98.817(2)^{\circ}$, Z = 2.

Metal Complexes of Ambidentate Ligands (Ⅲ). Palladium (Ⅱ) Complexes of Isonitrosobenzoylacetone Imine Derivatives (Ambidentate 리간드의 금속착물 (제 3보). Isonitrosobenzoylacetone Imine 유도체와 팔라듐(Ⅱ)의 착물)

  • Tae Sub O;Man Ho Lee;Su Han Kim;Jung Hak Park;Hae Woon Lee
    • Journal of the Korean Chemical Society
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    • v.26 no.1
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    • pp.31-35
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    • 1982
  • Novel palladium(II) complexes of the type Pd(IBA-NH)(IBA-NH') and Pd(IBA-NR)2, where IBA-NH and IBA-NR (R: methyl, ethyl, n-propyl, n-butyl, benzyl) represent isonitrosobenzoylacetone imine and its N-alkyl derivatives respectively, have been prepared. The ir, nmr, and electronic spectra of the palladium(Ⅱ) complexes have been studied. It has been determined that the isonitroso group of IBA-NH coordinates to palladium through the oxygen to form 6-membered chelate ring and that of IBA-NH' coordinates to palladium through the nitrogen to form 5-membered ring in square-planar Pd(IBA-NH)(IBA-NH') and it also has been determined that the isonitroso groups of two IBA-NR coordinates to palladium through the nitrogen to form 5-membered rings in square-planar Pd$(IBA-NR)_2$. The coordination manner of the ligands is similar to that of isonitrosoacetylacetone imines obtained by Bose, et $al.^5$.

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Catalytic Enantioselective Fluorination Reactions of α-Cyano Acetates and α-Cyanophosphonates Using Chiral Palladium Complexes

  • Kim, Sun-Mi;Kang, Young-Ku;Cho, Min-Je;Mang, Joo-Yang;Kim, Dae-Young
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2435-2441
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    • 2007
  • The catalytic enantioselective electrophilic fluorinations of active methane compounds promoted chiral palladium complexes have been developed. Treatment of α-cyano acetates and α-cyanoalkylphosphonates with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding α-cyano-α-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

The Effect of Electron-withdrawing Group Functionalization on Antibacterial and Catalytic Activity of Palladium(II) Complexes

  • Feng, Zhi-Qiang;Yang, Xiao-Li;Ye, Yuan-Feng;Hao, Lin-Yun
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1121-1127
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    • 2014
  • The design, synthesis, and structural characterization of two new palladium complexes based on Schiff base ligands is reported; $[Pd(L1)_2]$ (1) and $[Pd(L2)_2]$ (2), [HL1 = 2-((E)-(2,6-diethylphenylimino)methyl)-4,6-dibromophenol, L2 = (E)-N-benzylidene-2,6-diethylbenzenamine], which are obtained by functionalizing Schiff base ligands with or without electron-withdrawing groups. Both compounds are mononuclear structures. Comparisons are made to the compounds 1 and 2 to analyze and understand the effect of electron-withdrawing groups. Antibacterial activity studies indicate the electron-withdrawing groups on Schiff base ligands enhance antibacterial activity. Catalytic activity, however, is reduced due to the enhanced steric-hindrance of the electron-withdrawing groups. Electronic absorption and emission properties of HL1, L2, 1 and 2 are also reported.

Synthesis, Structures, and Catalytic Properties of Ionic Metallacyclodimeric Palladium(II) Complexes

  • Kim, Sung Min;Park, Kyung Hwan;Lee, Haeri;Moon, So Yun;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4069-4073
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    • 2012
  • Metallacyclodimeric complexes of $[(Me_4en)Pd(L)]_2(ClO_4)_4$ ($Me_4en$ = N,N,N',N'-tetramethylethylenediamine; L = dimethylbis(4-pyridyl)silane (dmps), methylvinylbis(4-pyridyl)silane (mvps)) have been synthesized, and their structures have been characterized by X-ray single crystallography. The skeletal structures consist of one 20-membered metallamacrocycle, two 5-membered metallacycles, and four pyridyl groups. The local geometry around the palladium(II) ion approximates to a typical square planar arrangement with four nitrogen donors. Delicate difference in catalytic effects on hydrogenation was investigated based on the structure of catalyst and substrates.

Enantioselective Fluorination of β-Keto Phosphonates and β-Ketoesters Catalyzed by Chiral Palladium Complexes

  • Lee, Na-Ri;Kim, Sun-Mi;Kim, Dae-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.4
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    • pp.829-836
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    • 2009
  • The catalytic enantioselective electrophilic fluorinations of active methine compounds promoted chiral palladium complexes have been developed. Treatment of $\beta$-keto phosphonates and $\beta$-ketoesters with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding $\alpha$-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

Syntheses and Theoretical Study of Palladium(II) Complexes with Aminophosphines as 7-Membered Chelate Rings

  • 김봉곤;양기열;정맹준;이배욱;도명기
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1162-1166
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    • 1997
  • Nature of palladium(Ⅱ) complexes with 7-membered chelates was studied by experimental and theoretical methods on a Pd(L)Cl2 system, where L is Ph2PNHCH2CH2NHPPh2(L1), Ph2PNHC6H4NHPPh2(L2). The palladium(Ⅱ) complexes were prepared and characterized by elemental analysis, IR, UV, 1H, and 31P NMR spectroscopy. Ab initio calculations with geometry optimizations were also performed for related model systems, Pd(L)Cl2; L=R2PNH(CH2)2NHPR2(L3), R2PNHC6H4NHPR2(L4), R2P(CH2)4PR2(L5), R2PCH2(C6H4)CH2PR2(L6); R=H, CH3.

Preparation of Dioxygen Bridged Palladium Complexes by Superoxide Ion $(O_2^-)$ (초과산화이온 $(O_2^-)$ 에 의한 산소가교팔라듐착화합물의 합성)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.135-142
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    • 1984
  • New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

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Determination of Pd(II) and Pt(II) Metal Cyano Complexes Using Capillary Electrophoresis

  • Lee, Hue-Jin;Lee, Sang-Ho;Chung, Koo-Soon;Lee, Kwang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.945-949
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    • 1994
  • Mixtures of cyano complexes of palladium(II) and platinum(II) were separated by capillary electrophoresis using a fused silica capillary as a separation column and 30 mM phosphate buffer (pH 7) containing 15 wt. % acetonitrile as a running buffer. By virtue of the high ionic mobilities of the negatively charged cyano complexes of Pd(II) and Pt(II), they were separated using a cathodic injection and anodic detection scheme. The metal complexes eluted through the capillary were detected by direct UV absorption at 214 nm. A linear relationship between peak area and concentration was obtained for both ions and the detection limit was lower than $10^{-14}$ mole. The proposed method was applied to real sample, e.g., anode slime obtained from an electrolytic copper refinary, as a method for the simultaneous determination of palladium and platinum.