• Title/Summary/Keyword: Ir(III) complex

Search Result 70, Processing Time 0.031 seconds

Asymmetric Ring Opening of Terminal Epoxides Catalyzed by Chiral Co(III)-BF3 Salen Complex Immobilized on SBA-16

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.8
    • /
    • pp.1771-1777
    • /
    • 2009
  • The homogeneous B$F_3$ containing chiral Co(III) salen complexes were anchored non-covalently on the surfaces of mesoporous SBA-16 silica containing aluminum species. The Brönsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. The FT-IR, UV, ESCA, and NMR analyses were performed to determine the structure of synthesized chiral salen catalysts. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by water and phenol derivatives. They showed very high enantioselectivity and yield more than 98% in the catalytic synthesis of optically active products.

Synthesis and Characterization of Dinuclear Ni(II) Complexes with Tetraazadiphenol Macrocycle Bearing Cyclohexanes

  • Kim, Ki-Ju;Jung, Duk-Sang;Kim, Duk-Soo;Choi, Chi-Kyu;Park, Ki-Min;Byun, Jong-Chul
    • Bulletin of the Korean Chemical Society
    • /
    • v.27 no.11
    • /
    • pp.1747-1751
    • /
    • 2006
  • The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.

The Complex Formation of p-Aminoazobenzene and its Derivatives with Fe(Ⅲ) and Mn(Ⅱ) in Organic Solvents (유기용매중에서 Fe(Ⅲ), Mn(Ⅱ)과 p-aminoazobenzene 및 그 유도체와의 착물형성에 관한 연구)

  • Eun Soo Kim
    • Journal of the Korean Chemical Society
    • /
    • v.32 no.5
    • /
    • pp.464-475
    • /
    • 1988
  • The complex formation of p-aminoazobenzene and its derivatives with Fe(III) and Mn(II) has been studied by UV and IR spectroscopy and conductometry. The effects of solvents, donor basicity, and other factors on the formation of these complexes have been examined. The vatio of metal to ligand for the complexes formed is 1 : 1, both in the solid state and in solution. The stability constants of Fe(III)-donor and Mn(II)-donor complexes are in the range of 10$^2$∼10$^4$ and 0.1∼1, respectively. The absorptivities are ~10$^4$ and ∼10$^3$ l/mol${\cdot}$cm respectively. Thermodynamic properties such as ${\Delta}H^{\circ}$, ${\Delta}G^{\circ}$ and ${\Delta}S^{\circ}$ are calculated from their stability constants utilizing Van't Hoff equation.

  • PDF

Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes

  • Chin, Chong-Shik;Won, Gyong-Shik;Song, Joong-Ho
    • Bulletin of the Korean Chemical Society
    • /
    • v.15 no.11
    • /
    • pp.961-966
    • /
    • 1994
  • Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

Chromium(III) Complex Obtained from Dipicolinic Acid: Synthesis, Characterization, X-Ray Crystal Structure and Electrochemical Studies

  • Ghasemi, Khaled;Rezvani, Ali Reza;Razak, Ibrahim Abdul;Moghimi, Abolghasem;Ghasemi, Fatemeh;Rosli, Mohd Mustaqim
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.10
    • /
    • pp.3093-3097
    • /
    • 2013
  • The synthesis, X-ray crystallography, spectroscopic (IR, UV-vis), and electrochemical properties of the title compound, $[H_3O][Cr(dipic)_2][H_3O^+.Cl^-]$ (1), ($H_2dipic$ = 2,6-pyridinedicarboxylic acid), are reported. This complex crystallizes in the monoclinic space group Cc with a = 14.9006(10) ${\AA}$, b = 12.2114(8) ${\AA}$, c = 8.6337(6) ${\AA}$, ${\alpha}=90.00^{\circ}$, ${\beta}=92.7460(10)^{\circ}$, ${\gamma}=90.00^{\circ}$, and V = 1569.16(18) ${\AA}^3$ with Z = 4. The hydrogen bonding and noncovalent interactions play roles in the stabilization of the structure. In order to gain a better understanding of the most important geometrical parameters in the structure of the complex, atoms in molecules (AIM) method at B3LYP/6-31G level of theory has been employed.

Synthesis, Characterization and in vitro Antibacterial Studies on Mixed Ligand Complexes of Iron(III) Based on 1,10-phenanthroline

  • Tigineh, Getinet Tamiru;Sitotaw, Getu;Workie, Amogne;Abebe, Atakilt
    • Journal of the Korean Chemical Society
    • /
    • v.65 no.3
    • /
    • pp.203-208
    • /
    • 2021
  • As part of our attempt to discover novel active compounds against multi-drug resistant pathogens, we hereby report two new complexes of iron(III) with formulae: [Fe(L1)2(H2O)2]Cl3 and [Fe(L1)2(L2)(H2O)]Cl2 where L1 = 1,10-phenanthroline (C12H8N2) and L2 = guanide (C5H4N5O-). The synthesized complexes were characterized using spectroscopic analysis (ESI-MS, ICP-OES, FT-IR, and UV-Vis), cyclic voltammetry, CHN analysis, gravimetric chloride determination, melting point determination, and conductance measurement. Octahedral geometries are assigned to both complexes. In vitro antibacterial activity was tested on two Gram-positive (Staphylococcus aureus, Streptococcus epidermidis) and two Gram-negative (Escherichia coli and Klebsiella pneumoniae) bacteria using the disc diffusion method. The complexes demonstrated appreciable activity against these pathogens. Interestingly, the [Fe(L1)2(L2)(H2O)]Cl2 complex manifested a higher degree of inhibition against the drug-resistant Gram-negative bacteria than the commercially available drug, namely erythromycin.

Electrochemical Properties of Diiron Complexes wish Conjugated Chains (공액 사슬을 갖는 철 화합물의 전기화학적 특성)

  • ;Micheal b. Sponsler
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
    • /
    • v.15 no.6
    • /
    • pp.511-517
    • /
    • 2002
  • The complex 1 $([Cp*Fe(CO)_2]_2-(\mu-CH=CH-CH=CH))$ which have butadiene as a bridge were synthesized from $Cp*(CO)_2FeK$ and cis-3,4-dichlorocyclobutene. The derivatives of complex 1 where one or two carbonyl groups are replaced by phosphine ligands have been prepared by photochemical substitution. The new derivatives $([Cp*Fe(L)_2]_2-(\mu-CH=CH-CH=CH))$ where L = $(Ph_2PCH_2CH_2PPh_2)$ and $([Cp*Fe(CO)(L)]_2-(\mu-CH=CH-CH=CH))$ where L : $PPh_3$ have been characterized from $^^1H-$, $^^13C-$,$^^31P-NMR$ and elemental analysis. Obtained complexes have been studied in electrochemical experiment and UV/VIS-near-IR. The mixed-valence radical cation forms of complex 2, 3 species were found to be delocalized as the Class III. Based on the separation of the waves ($\triangle E$ : 0.470 ~ 0.605 V), the efficiency of electronic communication between two metal centers of cation species leading to stabilization relative to neutral species. The phosphine-substitute complexes (2, 3) displays two reversible oxidation waves and oxidation state of metal centers-dependent color change, electrochromism, was observed from yellow to orange and deep blue in methylene chloride.

Complexation of Omeprazole with Meglumine and its Stability (오메프라졸과 메글루민의 복합체 형성과 안정성)

  • Lee, Gye-Ju;Kim, Sung-Wook;Do, Ki-Chan;Park, Chong-Bum;Hwang, Sung-Joo
    • Journal of Pharmaceutical Investigation
    • /
    • v.27 no.4
    • /
    • pp.253-263
    • /
    • 1997
  • To investigate the interaction of omeprazole (OMP) and meglumine (MEG), a complex was prepared by freeze-drying method in ammoniacal aqueous medium at room temperature and subjected to IR, DSC, and 1H NMR analysis. In addition, the stability of the complex was tested by accelerated stability analysis, and the dissolution rate of both powder and enteric coated was determined pellet by paddle method. The results are as follows; i) IR, DSC, and $^{1}H$ NMR studies indicate the formation of inclusion complex between OMP and MEG probably by electrostatic forces as $[OMP]\;[MEGH]^+$ form in a stoichiometric ratio (1:1) of OMP : MEG. ii) The dissolution rate of enteric coated OMP-MEG complex pellet in simulated enteric fluid was 90.6% in 10 minutes, which may satisfy the requirement for the regulation of dissolution. iii) OMP-MEG complex were decomposed according to pseudo 1st order kinetics: while the decomposition of OMP showed a rate constant $(k_{25^{\circ}C})$ of $5.13{\times}10^{-4}{\cdot}\;day^{-1}$, a half-life$(t_{1/2})$ of 1,350 days, a shelf-life$(T_{90%})$ 205 days and an activation energy of 23.53 kcal/mole. OMP-MEG complex inhibited a rate $(k_{25})$ of $2.92{\times}10^{-4}{\cdot}\;day^{-1}$, a half-life$(t_{1/2})$ of 2,373 days, a shelf-life $(T_{90%})$ of 306 days and an activation energy of 20.18 kcal/mole. iv) OMP was stabilized markedly by the formation of OMP-MEG complex between OMP and MEG, and the humidity increased the stability of OMP-MEG complex by decreasing the decomposition rate$(k_{50^{\circ}C})$ from $1.27{\times}10^{-2}{\cdot}\;day^{-1}$ at 31% R.H. to $2.54{\times}10^{-2}{\cdot}\;day^{-1}$ at 90% R.H.

  • PDF

Thermodynamic, Infrared, and Magnetic Studies on the Complexation of Gd(III) by Benzoate Anion (Gadolinium-benzoate 착물의 열역학적, 적외선 및 자기적 성질에 관한 연구)

  • Young-Inn Kim;Heung-Jae Park;Sung-Nak Choi;Sock-Seung Yun
    • Journal of the Korean Chemical Society
    • /
    • v.36 no.2
    • /
    • pp.212-217
    • /
    • 1992
  • The thermodynamic parameters for the formation of gadolinium benzoate have been determined in the ionic medium of 0.1 M $NaClO_4$ at $25^{\circ}C$ in aqueous solution. The thermodynamic results indicate that the complex is stabilized by the excess entropy effect caused by the dehydration of reacting ions. The especially high stability of Gd(III)-benzoate compared to the monodentate ligand complexes might be ascribed to the conjugation effect of the benzene ring in the benzoate ligand. IR spectra show that benzoate anion acts as a bidentate ligand toward $Gd^{3+}$ to form a chelate ring in solid state. Magnetic susceptibility data of the compound were also obtained and well described by Curie-Weiss law in the temperature range 80${\sim}$300K.

  • PDF

Synthesis, Potentiometric, Spectral Characterization and Microbial Studies of Transition Metal Complexes with Tridentate Ligand (세자리 리간드의 전이금속 착물에 대한 합성과 전위차 및 분광학적 확인 그리고 미생물학적 연구)

  • Jadhav, S.M.;Munde, A.S.;Shankarwar, S.G.;Patharkar, V.R.;Shelke, V.A.;Chondhekar, T.K.
    • Journal of the Korean Chemical Society
    • /
    • v.54 no.5
    • /
    • pp.515-522
    • /
    • 2010
  • A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.