• Title/Summary/Keyword: Carborane

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Synthesis and Characterization of Air Stable σ-Bonded ortho-carborane Manganese Metal Complexes $1-[Mn(CO)_5]-2-R-1,2-closo-(σ-C_2B_{10}H_{10}$ and Their Conversion to the Stable ortho-carborane Substituted Fischer-type Carbene Compexes 1-[(CO

  • 김세진;김유혁;고재정;강상욱
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.634-641
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    • 1995
  • The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

Bis(morpholine)-substituted 1,3,5-Triazines Derivatives: Synthesis and Structural Study

  • Lee, Jong-Dae
    • Journal of Integrative Natural Science
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    • v.11 no.2
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    • pp.61-68
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    • 2018
  • New 4,4'-[6-(o-carboranylalkoxy)-1,3,5-triazine-2,4-diyl]dimorpholine derivatives have been prepared by reacting 4,4'-[6-(alkynyloxy)-1,3,5-triazine-2,4-diyl]dimorpholines with decaborane and N,N-dimethylaniline as base. The intermediate compounds, 4,4'-[6-(alkynyloxy)-1,3,5-triazine-2,4-diyl]dimorpholines, have been prepared by reacting 4,4'-[6-chloro-1,3,5-triazine-2,4-diyl]dimorpholines with prop-2-yn-1-ol, but-3-yn-1-ol, and pet-4-yn-1-ol, and potassium tert-butoxide (t-BuOK) as base. The structure of these compounds has been confirmed by IR, $^1H$, $^{11}B$, and $^{13}C$ NMR and X-ray crystallographic studies.

A PHOTOCHEMICAL REACTION OF DECABORANE WITH TRIMETHYLSILYLDIAZOMETHANE

  • Sung, Dae-Dong;Kim, Chang-Soo;Lee, Jae-Duck;Lim, Gui-Taek;Uhm, Tae-Seop;Park, Yong Tae
    • Journal of Photoscience
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    • v.1 no.2
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    • pp.89-94
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    • 1994
  • The reaction of decaborane with trimethylsilyldiazomethane gives 1, 2-bis (trimethylsilyl)-1, 2-carba-closo-dodecaborane(12). This compound is similar to the icosahedral cage structure of o-carborane. This formation of the first adduct proceeds through deprotonation of the acidic center of B(9) and B(6) by intermolecular attack by the lone electron pair of the carbene, : CHSiMe$_3$. The yield of product is influenced by irradiation and thermal conditions.

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Preparation of Boronated Heterocyclic Compounds Using Intramolecular Cyclization Reaction

  • Lee, Chai-Ho;Jin, Guofan;Kim, Hyo-Suk;Nakamura, Hiroyuki;Chung, Yong-Seog;Lee, Jongdae
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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    • pp.357-362
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    • 2008
  • A method for synthesizing o-carborane substituted tetrahydroisoquinolines containing a polar functional group such as sulfamide, sulfonic, or phosphoric acid on the nitrogen atom of the piperidine ring, starting from arylethylamine, N-(2-arylethyl)sulfamide, N-(2-arylethyl)sulfamic acid or 2-arylethylamidophosphate, is described. In vitro studies showed the desired compounds 10, 15, 19, and 25 synthesized accumulate to high levels in B-16 melanoma cells with low cytotoxicity.

A Study on the Reaction of Icosahedral Carborane with Carbenes

  • Sung, Dae-Dong;Lee, Jae-Duck;Choi, Soon-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.63-68
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    • 1987
  • The photolysis and thermal reaction of hexafluorobenzene solution of icosahedral dicarba-closo-dodecaborane and various carbenes have been shown to lead to the formation of four isomeric insertion products to icosahedral molecules. The results showed the carbene insertion reaction to 1, 2-dicarba-closo-dodecaborane to occur at the positions of 4-, 5-, 7-, and 11-borons, 9-, and 12-borons 3-, and 6-borons and 8-, and 10-borons. The samples of 1, 7-, and 1, 12-dicarba-closo-dodecaborane with carbenes in hexafluorobenzene by photolysis showed no reaction. To find out the reactivities of carbenes to dicarba-closo-dodecaboranes, the total energies have been calculated and have been discussed the tendency for carbene insertion reactions to icosahedral carboranes.