• Title/Summary/Keyword: Metal complexes

Search Result 666, Processing Time 0.025 seconds

Theoretical Study of the Conformation of Cis Carbene-Olefin Transition Matal Complexes (시스 카벤-올레핀 전이금속 착물들의 형태에 대한 이론적 연구)

  • Seong-Kyu Park;Ill-Doo Kim;Joon-Tae Kim;Chang-Jin Choi;Young-Gu Cheun
    • Journal of the Korean Chemical Society
    • /
    • v.36 no.6
    • /
    • pp.802-811
    • /
    • 1992
  • The conformations of several carbene-olefin-transition metal complexes[$(CO)_4M$-(CHX)olefin] (X: $OCH_3,\;NHCH_3,\;SCH_3$, M: C, Mo, W) have been studied by means of Extend Huckel calculations. In the case of $d^6$ transition metal octahedral complexes, it is shown that the two main factors which determine the optimal conformation are metal-to-ligand back-donation and direct ligand-ligand interaction at the metal, but the ligand-ligand interaction dominates the situation for a metal that is coordinated to $\pi$ acceptor ligands and to $\pi$ donor group on the carbene. The relative amounts of both factors depend strongly on the electronic nature of the ligands at the metal. The greater electron donating ability of nitrogen stabilizes amino-substituted carbene complexes compared with their alkoxyl substituted analogues. This interaction is optimal when the $\pi$ systems of the carbene and olefin are coplanar. The introduction of the $\pi$ donor group on the carbene carbon increases also the importance of the ligand-ligand interaction.

  • PDF

Silver Up-Take by Modified Pitches

  • Manocha, Satish M.;Patel, Mitesh
    • Carbon letters
    • /
    • v.3 no.1
    • /
    • pp.13-16
    • /
    • 2002
  • The modification of coal-tar pitch has been carried out by heat treatment of pitch at different temperatures in the range ($300^{\circ}-400^{\circ}C$) for different times (2-5 hrs) in air and nitrogen. The pitch heat treated in air at lower temperature ($300^{\circ}C$) exhibit increase in softening point by $20^{\circ}C$ as compared to only $2^{\circ}C$ when treated in nitrogen. The changes are faster in air than in pure nitrogen. Pitch as such as well as after heat treatment were further treated with metal complexes by solution route. Silver intake has been found to increase from 0.5 to 0.8 % in nitrogen treated pitch while the uptake is found to decrease for pitches treated in air at $350^{\circ}C$ for 5 hrs. Experiments have also been made to incorporate silver into PAN and PAN-ox fibers through solution route. The metal intake has been found to be more in PAN-ox fibers than in PAN as such. Metal loaded carbon composites have been made by using metal loaded fibers as well as cokes. These composites as such exhibit higher surface oxygen complexes but decrease after activation.

  • PDF

Development and Application of Group IV Transition Metal Oxide Precursors

  • Kim, Da Hye;Park, Bo Keun;Jeone, Dong Ju;Kim, Chang Gyoun;Son, Seung Uk;Chung, Taek-Mo
    • Proceedings of the Korean Vacuum Society Conference
    • /
    • 2014.02a
    • /
    • pp.303.2-303.2
    • /
    • 2014
  • The oxides of group IV transition metals such as titanium, zirconium, hafnium have many important current and future application, including protective coatings, sensors and dielectric layers in thin film electroluminescent (TFEL) devices. Recently, group IV transition metal oxide films have been intensively investigated as replacements for SiO2. Due to high permittivities (k~14-25) compared with SiO2 (k~3.9), large band-gaps, large band offsets and high thermodynamic stability on silicon. Herein, we report the synthesis of new group IV transition metal complexes as useful precursors to deposit their oxide thin films using chemical vapor deposition technique. The complexes were characterized by FT-IR, 1H NMR, 13C NMR and thermogravimetric analysis (TGA). Newly synthesised compounds show high volatility and thermal stability, so we are trying to deposit metal oxide thin films using the complexes by Atomic Layer Deposition (ALD).

  • PDF

Synthesis and Electronic Properties of Dicarbonyltetrakis(triphenylphosphine) Complexes of Molybdenum(0) and Tungsten(0) (디카르보닐테트라키스 몰리브데늄(0)과 텅스텐(0) 착물들에 대한 합성과 전자적 성질에 관한 연구)

  • Choi, Chil Nam;Kim, Sun Kyu
    • Journal of the Korean Chemical Society
    • /
    • v.44 no.3
    • /
    • pp.194-199
    • /
    • 2000
  • The chemical behavior for Mo(0) and W(0) complexes, [M(CO)$_2$(PPh$_3$)$_4$] (M=Mo and W),has been investigated by UV-vis spectroscopic, magnetic, and electrochemical methods. Three absorption bands are observed in the UV-spectra. The crystal-field-splitti ng energy, spin-pairing energy, and bond strengths were deduced from the spectra. The metal d electrons in both complexes seemed to be delocalized in low-spin state.Metal ligand correlation appeared to strongly depend on bond strengths and diamagnetic properties. In electrochemical processes, both complexes exhibit an irreversible reduction wave.

  • PDF

Synthesis and Characterization of Transition Metal Complexes with Benzimidazolyl-2-hydrazones of o-anisaldehyde and Furfural

  • Mohapatra, R.K.;Mishra, U.K.;Mishra, S.K.;Mahapatra, A.;Dash, D.C.
    • Journal of the Korean Chemical Society
    • /
    • v.55 no.6
    • /
    • pp.926-931
    • /
    • 2011
  • A series of complexes of the type [$ML_2Cl_2$], where L=2-(o-anisylidene-2'-imino) amino benzimidazole (AIAB) and 2-(furfurylidene imino) amino benzimidazole (FIAB), M=Cu(II), Co(II), Ni(II) and Zn(II), have been synthesized and characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, $^1H$-NMR spectral studies. The results are in consistent with bidentate chelation of ligand with azomethine nitrogen and ring nitrogen donors. All these Schiff bases and their complexes have also been screened for their antibacterial (Bacillus subtilis, Bacillus stearothermophilus, Escherichia coli and Salmonella typhi) and antifungal activities (Aspergillus niger and Aspergillus flavus).

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
    • /
    • v.15 no.11
    • /
    • pp.945-949
    • /
    • 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.

Effect of Transition Metal(II)-N,N-Bis(salicylaldehyde)phenylenediimines on the Electrochemical Reduction of Thionyl Chloride

  • 김현수;최용국;조기형;국성근;우희권
    • Bulletin of the Korean Chemical Society
    • /
    • v.17 no.3
    • /
    • pp.223-227
    • /
    • 1996
  • Catalytic effects of transition metal (Co2+, Ni2+) complexes of N,N-bis(salicylaldehyde)-o-phenylenediimine (SOPD), N,N-bis(salicylaldehyde)-m-phenylenediimine (SMPD), and N,N-bis(salicylaldehyde)-p-phenylenediimine (SPPD), on the reduction of thionyl chloride at glassy carbon electrode, are evaluated by determining the kinetic parameters with cyclic voltammetric technique. The charge transfer process for the reduction of thionyl chloride is strongly affected by the concentration of the catalysts. Some quadridentate Schiff base-M(Ⅱ) complexes show sizable catalytic activities for the reduction of thionyl chloride. Catalytic effects of [M(Ⅱ)(SOPD)] complexes are slightly larger compared to [M(Ⅱ)2(SMPD)2] and [M(Ⅱ)2(SPPD)2] complexes. On those electrodes deposited with the catalysts, the observed exchange rate constants (ko) are in the range of 0.89-2.28 × 10-7 cm/s, while it is 1.24 × 10-7 cm/s on the bare glassy carbon electrode.

Preparation and Crystal Structures of Silver(I), Mercury(II), and Lead(II) Complexes of Oxathia-Tribenzo-Macrocycles

  • Siewe, Arlette Deukam;Ju, Huiyeong;Lee, Shim Sung
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.3
    • /
    • pp.725-730
    • /
    • 2013
  • An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles $L^1-L^3$ ($L^1$: 20-membered $O_3S_2$, $L^2$: 20-membered $O_2S_3$, and $L^3$: 23-membered $O_4S_2$) with $d^{10}$-metal ($Ag^+$, $Hg^{2+}$, and $Pb^{2+}$) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of $L^2$ and $L^3$ with the silver(I) salts ($PF_6{^-}$ and $SCN^-$) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex $[Ag_2(L^2)_2](PF_6)_2{\cdot}3CH_2Cl_2$ (1) and a linear dinuclear complex $[Ag_2(L^3)_2(SCN)_2]$ (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of $L^1$ and $L^2$ with mercury(II) salts ($SCN^-$ and $Cl^-$) gave a mononuclear 1:1 complexes $[Hg(L^1)(SCN)_2]$ (3) and $[Hg(L^2)Cl_2]$ (4) with anion coordination in both cases. $L^2$ reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex $[Pb(L^2)_2(ClO_4)_2]$ (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.

Two 3D CdII and ZnII Complexes Based on Flexible Dicarboxylate Ligand and Nitrogen-containing Pillar: Synthesis, Structure, and Luminescent Properties

  • Liu, Liu;Fan, Yan-Hua;Wu, Lan-Zhi;Zhang, Huai-Min;Yang, Li-Rong
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.12
    • /
    • pp.3749-3754
    • /
    • 2013
  • Two 3D isomorphous and isostructural complexes, namely, $[Zn(BDOA)(bpy)(H_2O)_2]_n$ (1) and $[Cd(BDOA)-(bpy)(H_2O)_2]_n$ (2); (BDOA = Benzene-1,4-dioxyacetic acid, bpy = 4,4'-bipyridine) were synthesized under hydrothermal conditions and characterized by means of elemental analyses, thermogravimetric (TG), infrared spectrometry, and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic system, space group P-1 and each metal ion in the complexes are six-coordinated with the same coordination environment. In the as-synthesized complexes, $BDOA^{2-}$ anions link central metal ions to form a 1D zigzag chain $[-BDOA^{2-}-Zn(Cd)-BDOA^{2-}-Zn(Cd)-]_{\infty}$, whereas bpy pillars connect metal ions to generate a 1D linear chain $[-bpy-Zn(Cd)-bpy-Zn(Cd)-]_{\infty}$. Both infinite chains are interweaved into 2D grid-like layers which are further constructed into a 3D open framework, where hydrogen bonds play as the bridges between the adjacent 2D layers. Luminescent properties of complex 1 showed selectivity for $Hg^{2+}$ ion.

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
    • /
    • v.7 no.1
    • /
    • pp.107-113
    • /
    • 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.

  • PDF