• Title/Summary/Keyword: Bidentate

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Cu Catalyst System with Phosphorous Containing Bidendate Ligand for Living Radical Polymerization of MMA

  • Hong Sung Chul;Shin Ki Eun;Noh Seok Kyun;Lyoo Won Seok
    • Macromolecular Research
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    • v.13 no.5
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    • pp.391-396
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    • 2005
  • The polymerization of methyl methacrylate (MMA) was carried out using CuBr/bidentate phosphorus ligand catalyst systems. MMA polymerization with CuBr/phosphine-phosphinidene (PP) exhibited high conversion ($\~80\%$) in 5 h at $90^{\circ}C$ along with a linear increase of ln($[M]_0/[M]$) versus time, indicating constant concentration of the propagating radicals during the polymerization. The molecular weight of the prepared PMMA tended to increase with conversion, suggesting the living polymerization characteristic of the system. On the other hand, a large difference between the measured and theoretical molecular weight and a broad molecular weight distribution were observed, implicating possible incomplete control over the polymerization. This may have been caused by the low deactivation rate constant ($\kappa_{deact}$) of the system. The low $\kappa_{deact}$, would result in irreversible generation of radicals instead of reversible activation/deactivation process of ATRP. Polymerizations performed at different ligand to CuBr ratios and different monomer to initiator ratios did not afford better control over the polymerization, suggesting that the controllability of CuBr/phosphorus ligand system for ATRP is inherently limited.

Self-Assembled Structures of Glutaric Acid on Cu(110)

  • Park, Eun-Hui;Min, Yeong-Hwan;Kim, Se-Hun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.270-270
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    • 2013
  • We have investigated the self-assembled structures of glutaric acid (HOOC-(CH2)3-COOH) on the Cu(110) surface as a function of coverage using Scanning Tunneling Microscopy (STM). At low coverage, glutaric acid molecules diffuse freely on Cu(110) surface at room temperature, thus they can't form ordered structures at this coverage. However, when we scanned the same area several times, novel structures have been created during scanning due to the field-induced self-assembly. Also, the induced structures are quite stable during continuous scanning process. At 0.25 ML, glutaric acid adsorbs as a bi-glutarate (-OOC(CH2)3-COO-) after annealing to 450 K producing a racemic conglomerate of coexisting mirror domains. Although the molecule is achiral, it forms chiral domains on the surface from adsorption-induced asymmetrization. At 0.5 ML coverage, zigzag structure is observed, and still gltutaric acid adsorbs as a bidentate configuration. This bi-glutarate structure is stable until 650. Finally, at 1ML, glutaric acid adsorbs as a mono-glutarate at room temperature forming close packed structures.

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Monooxo-bridged Binuclear Molybdenum (V) Complexes (IV) (한 개 산소 가교 이핵몰리브덴 (V) 착물 (제4보))

  • Sang Oh Oh;Jong Dal Rhee
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.81-87
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    • 1982
  • The monooxo-bridged binuclear molybdenum(V) complexes, $Mo_2O_3(NCS)_4(Bipy)_2\;(Bipy = bipyridine),\;Mo_2O_3(NCS)-4(Phen)-2$ (Phen = 1,10-phenanthroline), and $Mo_2O_3(NCS)_4(Ox)_2(OxH)_2$ (Ox = oxinato and OxH = oxine) have been prepared. Their electronic and IR spectra, electric conductivity, and magnetic susceptibility were measured. From the results all of th complexes turned out to be electroneutral dimers with about 0.5 BM, and in the oxine complex, $Mo_2O_3(NCS)_2(Ox)_2(OxH)_2$, the oxine seems to bind partly as monodentate and partly as bidentate molecule.

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Spectroscopic Properties and Ligand Field Analysis of trans -Dibromo(2,2-dimethyl-1,3-diaminopropane)chromium(III) Moiety

  • Choi, Jong-Ha;Oh, In-Gyung;Lim, Woo-Taik;Ryoo, Keon-Sang;Kim, Dong-Il;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.903-908
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    • 2005
  • The sharp-line absorption and emission spectra of $(H_{13}O_6)${$trans-[Cr(Me_2tn)_2Br_2]$}$_2Br_2(ClO_4)\;(Me_2$tn = 2,2-dimethyl-1,3-diaminopropane) have been measured between 13000 $cm^{-1}$ and 16000 $cm^{-1}$ at 5 K. The 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex ion. The zero-phonon line in the sharp-line absorption spectrum splits into two components by 286 $cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the Me2tn ligand have a strong $\sigma$-donor character, but the bromide has weak $\sigma$- and $\pi$-donor properties toward chromium(III) ion.

Synthesis, Structure, and Magnetic Properties of 1D Nickel Coordination Polymer Ni(en)(ox)·2H2O (en = ethylenediamine; ox = oxalate)

  • Chun, Ji-Eun;Lee, Yu-Mi;Pyo, Seung-Moon;Im, Chan;Kim, Seung-Joo;Yun, Ho-Seop;Do, Jung-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1603-1606
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    • 2009
  • A new 1D oxalato bridged compound Ni(en)(ox)-2$H_2$O, (ox = oxalate; en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In the structure the Ni atoms are coordinated with four oxygen atoms in two oxalate ions and two nitrogen atoms in one ethylenediamine molecule. The oxalate anion acts as a bis-bidentate ligand bridging Ni atoms in cis-configuration. This completes the infinite zigzag neutral chain, [Ni(en)(ox)]. The interchain space is filled by water molecules that link the chains through a network of hydrogen bonds. Thermal variance of the magnetic susceptibility shows a broad maximum around 50 K characteristic of one-dimensional antiferromagnetic coupling. The theoretical fit of the data for T > 20 K led to the nearest neighbor spin interaction J = -43 K and g = 2.25. The rapid decrease in susceptibility below 20 K indicate this compound to be a likely Haldane gap candidate material with S = 1.

Synthesis, Characterization, DFT Modeling and Antimicrobial Studies on the Ti(IV), Y(III) and Ce(IV) Ofloxacin Solid Complexes

  • Sadeek, Sadeek A.;Zordok, Wael A.;El-Shwiniy, Walaa H.
    • Journal of the Korean Chemical Society
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    • v.57 no.5
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    • pp.574-590
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    • 2013
  • A new solid complexes of Ti(IV), Y(III) and Ce(IV) have been synthesized with ofloxacin. The formulae and structure of the complexes have been proposed in the light of analytical, spectral ($^1H$ NMR, IR and UV-Visible), magnetic, molar conductivities and thermal studies. The complexes are soluble in DMSO-$d_6$ and DMF. The measured molar conductance values indicate that, the three complexes are electrolyte in nature. The results support the formation of the complexes and indicated that ofloxacin reacts as a bidentate ligand chelate to the metal ion through the pyridone oxygen and one carboxylato oxygen. The kinetic parameters of thermogravimetric and its differential have been evaluated by using Coats Redfern (CR) and Horowitz-Metzeger (HM) methods. The thermodynamic data reflect the thermal stability for all complexes. The metal- ligand binding of the Ti(IV), Y(III) and Ce(IV) complexes is predicted using density funcational theory at the B3LYP-CEP-31G level of theory and total energy, dipole moment estimation of different Ti(IV), Y(III) and Ce(IV) ofloxacin structures. The biological activities of the ofloxacin, inorganic salts and their metal complexes were assayed against different bacterial species.

Studies on the Spectrophotometric Determination and Electrochemical Behavior of Heavy Lanthanide Ions in Nonaqueous System and Heavy Metal Chelate Complexes with Bidentate Legands: (Part I) Flow Injection Spectrophotometric Determination of Heavy Lanthanide Ions with Xylenol Orange

  • Sam-Woo Kang;Chong-Min Park;Kwang-Hee Cho;Hong-Seock Han
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.59-62
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    • 1993
  • Spectrophotometric determination of some heavy lanthanide ions by flow injection method is described. Xylenol Orange forms water soluble chelates with lanthanide ions in a tris[hydroxymethyl]-aminomethane-buffered medium having pH 8.3 and containing cetyltrimethylammonium bromide. The molar absorptivities of Ln(III)-XO complexes were increased by the ternary system with cetyltrimethylammonium bromide with the concomitant bathochromic shift of absorption maxium compared to those of the binary system without cetyltrimethylammonium bromide. The calibration curves are linear in the range 0.25-1.00 ppm for Gd(III), Dy(III), Er(III), Tm(III) and Yb(III) and the dynamic range are very wide. The detection limits (S/N=2) are from 2 ppb for Gd(III) to 30 ppb for Yb(III) and the relative standard deviations are from 1.2% for 0.5 ppm Gd(III) to 1.8% for 0.5 ppm Yb(III). The sample throughput was ca. 50 $h^{-1}$.

Di- and Triorganotin(IV) Complexes of Sulfur-containing Ylidenemalonates

  • Jung, Ok-Sang;Lee, Young-A;Hong, Jong-Ki;Jeong, Jong-Hwa;Sohn, Youn-Soo
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.722-726
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    • 1993
  • Organotin(IV) complexes of ylidenemalonates $(R_xSn)_{x-1}(O_2C)_2C=C(SR')_2\;(R=n-C_4H_9,\;C_6H_5,\;cyclo-C_6H_{11},\;CH_3OOCCH_2CH_2;\;x=2,3;\;R'=CH_3,\;R_2'=-CHCH-,\;-CH_2CH_{2^-})$ have been synthesized and characterized by means of various spectroscopic methods. The X-ray crystal structure of $(Ph_3Sn)_2(O_2C)_2C=C(SCH_3)_2$ has been determined (Pi; a= 9.704(2) ${\AA}$, b= 14.412(1) ${\AA}$, c= 14.760(3) ${\AA}$, ${alpha}$=74.26(1)$^{\circ}$, ${beta}$=99.38(l)$^{\circ}$, ${\gamma}$=79.09(1)$^{\circ}$, $V= 1950.7(7){\AA}^3$) and refined to R= 0.045. The crystal structure discloses a discrete molecule with bidentate-like carboxylate ligand. For diorganotin analogues, the structures are discussed in terms of IR, $^1H-NMR,\;^{13}C-NMR$, and FAB mass spectrometry. The mass spectrum indicates that the diorganotin complexes of ylidenemalonates are dimeric.

Li+ and Li+I-Li+ ions Solvated by 1,4-dioxane: An ion Mobility Spectrometry-Mass Spectrometry Study

  • Choi, Yunseop;Ji, Inyong;Seo, Jongcheol
    • Mass Spectrometry Letters
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    • v.12 no.4
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    • pp.152-158
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    • 2021
  • Electrospray ionization (ESI) and ion mobility spectrometry-mass spectrometry (IMS-MS) were employed to investigate the solvated structures of ionic species in the lithium iodide electrolyte solution in the gas phase. The Li+I-Li+ triple ion and single standalone Li+ ions solvated by 1,4-dioxane were successfully generated and observed by ESI-MS under the influence of dioxane vapor at the inlet region. Under the present experimental condition, (1,4-dioxane)m·Li+ complex ions (m = 1, 2, and 3) and a (1,4-dioxane)·Li+I-Li+ complex ion were observed, which were further examined by IMS to investigate their structures. The presence of multiple structural isomers was confirmed, which accounts for the endothermic conformational transition of 1,4-dioxane from a chair to a boat to achieve bidentate O-donor binding to Li+ and Li+I-Li+. Further structural details critical for the ion-solvent interactions were also examined and discussed with the help of density functional theory calculations.

Synthesis of New VO(II), Co(II), Ni(II) and Cu(II) Complexes with Isatin-3-Chloro-4-Floroaniline and 2-Pyridinecarboxylidene-4-Aminoantipyrine and their Antimicrobial Studies

  • Mishra, Anand P.;Mishra, Rudra;Jain, Rajendra;Gupta, Santosh
    • Mycobiology
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    • v.40 no.1
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    • pp.20-26
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    • 2012
  • The complexes of tailor made ligands with life essential metal ions may be an emerging area to answer the problems of multi drug resistance. The coordination complexes of VO(II), Co(II), Ni(II) and Cu(II) with the Schiff bases derived from isatin with 3-chloro-4-floroaniline and 2-pyridinecarboxaldehyde with 4-aminoantipyrine have been synthesized by conventional as well as microwave methods. These compounds have been characterized by elemental analysis, molar conductance, electronic spectra, FT-IR, FAB mass and magnetic susceptibility measurements. FAB mass data show degradation of complexes. Both the ligands behave as bidentate and tridentate coordinating through O and N donor. The complexes exhibit coordination number 4, 5 or 6. The Schiff base and metal complexes show a good activity against the bacteria; $Staphylococcus$ $aureus$, $Escherichia$ $coli$ and $Streptococcus$ $fecalis$ and fungi $Aspergillus$ $niger$, $Trichoderma$ $polysporum$, $Candida$ $albicans$ and $Aspergillus$ $flavus$. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases. The minimum inhibitory concentrations of the metal complexes were found in the range 10-40 ${\mu}g/mL$.