• Title/Summary/Keyword: o-Carborane

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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.

Synthesis and Characterization of Group VI Metal Carbonyl Complexes Containing closo-1,2-$(PPh_2)_2$-1,2-$C_2B_1_0H_1_0$ and Their Conversion to Metal Carbene Complexes

  • 박영일;김세진;고재정;강상욱
    • Bulletin of the Korean Chemical Society
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    • v.18 no.10
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    • pp.1061-1066
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    • 1997
  • The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

Oxidation of Tricarbonylmolybdacarborane.3.1 A New Entry to the First Examples of Sulfido-Bridged Dinuclear molybda(V)carboranes

  • Hwang, Jeong-Wook;Kim, Jae-Hak;Kim, Jin-Kwon;Uhm, Jae-Kook;Do, Young-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1257-1262
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    • 2002
  • $[(C_2B_9H_{11})Mo(CO)_3]_2PPN_2$ $(2{\cdot}PPN_2)$, a new precursor for the oxidative decarbonylation reaction, was synthesized in high yield by the one-electron oxidation reaction of $[(C_2B_9H_{11})Mo(CO)_3]PPN_2$. $2{\cdot}PPN_2$ was structurally characterized, showing a dimeric nature with long (3.321 ${\AA}$) Mo-Mo bonding. Reaction of $2{\cdot}PPN_2$ with sulfur gave the completely decarbonylated product $[(C_2B_9H_{11})Mo({\mu}-S)(S)]_2PPN_2$ ($3{\cdot}PPN_2$). The ligand substitution of the terminal sulfur ligands in $3{\cdot}PPN_2$ to oxygen ligands was carried out with the use of PhIO to give $[(C_2B_9H_{11})Mo({\mu}-S)(O)]_2PPN_2$ ($4{\cdot}PPN_2$). The structures of $3{\cdot}PPN_2$ and $4{\cdot}PPN_2$ were also studied.