• Title/Summary/Keyword: Organometallic bond

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Organometallic fluorine-18 bonds in 18F-radiochemistry

  • Joong-Hyun Chun;Minju Lee;Sungwon Jun;Jeongmin Son
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.7 no.1
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    • pp.22-32
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    • 2021
  • Fluorine-18 is by far the most widely exploited radionuclide in PET (positron emission tomography) radiochemistry. The physical half-life of fluorine-18 allows for chemical manipulation within a restricted timeframe, and cyclotron-produced fluoride ion has been widely applied in aliphatic and aromatic nucleophilic radiofluorinations to produce a variety of established radiotracers. Radiotracers have become more structurally complicated to address diverse targets in physiobiological systems. There is therefore an unmet need to complement traditional C-18F bond-forming radiofluorination with new and efficient radiolabeling techniques to tackle the myriad of possible chemical environments. This review discusses recent advances in organometallic fluorine-18 bond creation in 18F-radiochemistry. Although not widely employed, new radiolabeling strategies for constructing boron-18F, silicon-18F, aluminum-18F, and other metal-18F bonds are described in view of their potential use in the development of novel radiopharmaceuticals.

Annealing effects of organic inorganic hybrid silica material with C-H hydrogen bonds (C-H 수소결합을 갖는 유무기 하이브리드 물질에서의 열처리 효과)

  • Oh, Teresa
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.44 no.11
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    • pp.20-25
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    • 2007
  • In this paper, It was reported the dielectric constant in organic inorganic hybrid silica material such as SiOC film modeling of bond structure by annealing in organic properties. The organic inorganic hybrid silica material were deposited using bis-trimethylsilymethane (BTMSM, [(CH3)3Si]2CH2) and oxygen gas precursor by a plasma chemical vapor deposition (CVD). The organic inorganic hybrid silica material have three types according to the deposition condition. The dielectric constant of the films were performed MIS(Al/Si-O-C film/p-Si) structure. The C 1s spectra in organin inorganic silica materials with the flow rate ratio of O2/BTMSM=1.5 was organometallic carbon with the peak 282.9 eV by XPS. It means that organometallic carbon component is the cross-link bonding structure with good stability. The dielectric constant was the lowest at annealed films with cross-link bonding structure.

Molecular Orbital Studies of Bonding Characters of Al-N, Al-C, and N-C Bonds in Organometallic Precursors to AIN Thin Films

  • 이기학;박성수;이한명;박수진;박항수;이윤섭;김윤수;김세훈;조찬균;은희만
    • Bulletin of the Korean Chemical Society
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    • v.19 no.12
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    • pp.1314-1319
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    • 1998
  • Electronic structures and properties of the organometallic precursors [Me2AlNHR]2 (R =Me, iPr, and tBu) have been calculated by the semiempirical (ASED-MO, MNDO, AM1 and PM3) methods. Optimized structures obtained from the MNDO, AM1, and PM3 calculations indicate that the N-C bond lengths are considerably affected by the change of the R groups bonded to nitrogen, but the bond lengths of the Al-N and Al-C bonds are little affected. This result is useful in explaining the experimental results for the elimination of the R groups bonded to nitrogen, and could serve as a guide in designing an optimum precursor for the AlN thin film formation.

Density Functional Study on the C-H Bond Cleavage of Aldimine by a Rhodium(I) Catalyst

  • Yoo, Kyung-Hwa;Jun, Chul-Ho;Choi, Cheol-Ho;Sim, Eun-Ji
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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    • pp.1920-1926
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    • 2008
  • We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.

“Aluminium Nitride Technology-a review of problems and potential"

  • Dryburgh, Peter M.
    • Proceedings of the Korea Association of Crystal Growth Conference
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    • 1996.06a
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    • pp.75-87
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    • 1996
  • This review is presented under the following headings: 1.Introduction 1.1 Brief review of the properties of AlN 1.2 Historical survey of work on ceramic and single crystal AlN 2.Thermochemical background 3.Crystal growth 4.Doping 5.Potential applications and future work The known properties of AlN which make it of interest for various are discussed briefly. The properties include chemical stability, crystal structure and lattice constants, refractive indices and other optical properties, dielectric constant, surface acoustic wave velocity and thermal conductivity. The history of work in single crystals, thin films and ceramics are outlined and the thermochemistry of AlN reviewed together with some of the relevant properties of aluminium and nitrogen; the problems encountered in growing crystals of AlN are shown to arise directly from these thermochemical relationships. Methods have been reported in the literature for growing AlN crystals from melts, solution and vapour and these methods are compared critically. It is proposed that the only practicable approach to the growth of AlN is by vapour phase methods. All vapour based procedures share the share the same problems: $.$the difficulty of preventing contamination by oxygen & carbon $.$the high bond energy of molecular nitrogen $.$the refractory nature of AlN (melting point~3073K at 100ats.) $.$the high reactivity of Al at high temperatures It is shown that the growth of epitactic layers and polycrystalline layers present additional problems: $.$chemical incompatibility of substrates $.$crystallographic mismatch of substrates $.$thermal mismatch of substrates The result of all these problems is that there is no good substrate material for the growth of AlN layers. Organometallic precursors which contain an Al-N bond have been used recently to deposit AlN layers but organometallic precursors gave the disadvantage of giving significant carbon contamination. Organometallic precursors which contain an Al-N bound have been used recently to deposit AlN layers but organometallic precursors have the disadvantage of giving significant carbon contamination. It is conclude that progress in the application of AlN to optical and electronic devices will be made only if considerable effort is devoted to the growth of larges, pure (and particularly, oxygen-free) crystals. Progress in applications of epi-layers and ceramic AlN would almost certainly be assisted also by the availability of more reliable data on the pure material. The essential features of any stategy for the growth of AlN from the vapour are outlined and discussed.

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ONIOM and Its Applications to Material Chemistry and Catalyses

  • Morokuma, Keiji
    • Bulletin of the Korean Chemical Society
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    • v.24 no.6
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    • pp.797-801
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    • 2003
  • One of the largest challenges for quantum chemistry today is to obtain accurate results for large complex molecular systems, and a variety of approaches have been proposed recently toward this goal. We have developed the ONIOM method, an onion skin-like multi-level method, combining different levels of quantum chemical methods as well as molecular mechanics method. We have been applying the method to many different large systems, including thermochemistry, homogeneous catalysis, stereoselectivity in organic synthesis, solution chemistry, fullerenes and nanochemistry, and biomolecular systems. The method has recently been combined with the polarizable continuum model (ONIOM-PCM), and was also extended for molecular dynamics simulation of solution (ONIOM-XS). In the present article the recent progress in various applications of ONIOM and other electronic structure methods to problems of homogeneous catalyses and nanochemistry is reviewed. Topics include 1. bond energies in large molecular systems, 2. organometallic reactions and homogeneous catalysis, 3. structure, reactivity and bond energies of large organic molecules including fullerenes and nanotubes, and 4. biomolecular structure and enzymatic reaction mechanisms.

Dehydrogenative Polymerization of Hydrosilanes to Silicon Polymers

  • Kim, Myoung-Hee;Lee, Jun;Mo, Soo-Yong;Kim, Jong-Hyun;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.3 no.2
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    • pp.61-71
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    • 2010
  • Hydrosilanes possessing reactive Si-H bond are used in synthesizing various types of polysilanes by dehydrocoupling under the influence of various organometallic promoters. Catalytic Si-Si/Si-O coupling of hydrosilanes with hydrosilanes, alcohols, and lactones to silicon-based polymers are described in this article as selective examples of our recent research developments. These silicon-containing polymers can be used as a precursor to prepare useful functional materials for fabricating electronic devices.

Synthesis and Properties of Poly[4,4-bis(acetoxymethyl)-1,6-heptadiyne]

  • Kim, Yun-Hi
    • Bulletin of the Korean Chemical Society
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    • v.18 no.1
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    • pp.66-70
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    • 1997
  • The polymerization of 4, 4-bis(acetoxymethyl)-1, 6-heptadiyne (BAH) was carried out by MoCl5 and WCl6 with various organometallic cocatalysts. MoCl5-based catalysts were more effective than WCl6-based ones for the cyclopolymerization of BAH. Poly(BAH) was characterized to have polymer backbone with conjugated double bond and cyclic structure by IR, UV-visible, and 1H-and 13C NMR spectroscopies. The polymer was stable up to 310 ℃ and 5 % weight loss show up at 350 ℃. The resulting dark violet polymer exhibited good solubility in common organic solvents and could be cast on a glass plate to give film with good mechanical properties. It was found that oxygen permeability (PO2) and permselectivity (PO2/PN2) of the resulting polymer were 15.2 barrer and 2.84, respectively.

Geometries and Relative Stabilities of AlN Four-Membered-Ring Compound Isomers: Ab initio Study

  • Park, Sung-Soo;Lee, Kee-Hag;Suh, Young-Sun;Lee, Chang-Hoon;Luthi, Hans P.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.241-244
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    • 2002
  • Using ab initio method, we have studied the structural stabilities, the electronic structures and properties between the two isomers with $C_{2h}$ and $C_{2v}$ symmetry of AlN four-membered-ring single precursors $[Me_2AlNHR]_2$ (R = Me, $^iPr$, and $^iBu$). In the viewpoint of bond lengths in optimized structures, the N-C bonds are considerably affected by the change of the R groups bonded to nitrogen, but the bonding characters of the Al-N and Al-C bonds are little affected. Also the structural stabilities between the two isomers with $C_{2h}$ and $C_{2v}$ symmetry by using Hartree-Fock (HF) and the second order Moeller-Pleset (MP2) calculations agree well with the experimental results for the relative stability of bis(dimethyl- m-isopropylamido-aluminum) (BDPA) and bis(dimethyl- m-t-butylamido-aluminum) (BDBA), while the semiempirical AM1 and PM3 calculations for BDPA were reverse. Thus, our results may aid in designing an optimum precursor for a given process by explaining the experimental results through the elimination of the R groups bonded to nitrogen.

Coordination Polymerization of Carbon Double Bond Catalyzed by Organometallic Compounds (유기금속화합물 촉매에 의한 탄소이중결합의 배위중합)

  • Lee Dong-ho
    • Polymer(Korea)
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    • v.29 no.4
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    • pp.321-330
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    • 2005
  • In 1990's the Korean polyolefin industry boomed up through the development of magnificient polymerization catalysts. To understand the general situation of polymerization catalyst R & D, the various experimental results had been summarized for the investigation of not only the supported Ziegler-Natta catalyst used presently in polyolefin industry but also the metallocene catalysts applied for the preparation of special grade of polyolefin. In addition, it had been shown that the new polymeric materials were prepared by new developed catalyst, and the polymer in-situ nanocomposites could be obtained with the application of catalyst heterogenization procedures.