Polyhedral-based nonlinear optical materials. 3. Synthetic studies of cyclopentadiene- and cycloheptatriene-substituted polyhedral compounds: Synthesis of 1,12-[(C7H7)C2B10H10 (C5H3Me2)] and related species

J. Taylor, J. Caruso, A. Newlon, Ulrich Englich, Karin Ruhlandt, James T Spencer

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The synthesis and characterization of a series of new olefin-substituted closo-1,12-[C2B10H12] compounds is described. The reaction of deprotonated closo-1,12-dicarbadodecaborane with 7-methoxycycloheptatriene yields the cycloheptatriene-substituted carborane compound, closo-[1-(1-C7H7)-12-(H) -C2B10H10] (3). Deprotonation of 3 with butyllithium and subsequent reaction with 3,4-dimethyl-2-cyclopenten-1-one was found to yield the bis- olefin-substituted carbinol compound [1-(1-C7H7)-12-(C5H41-(OH) -3,4-(CH3)2)-C2B10H10] (5) in good yield. Acidic dehydration of 5 quantitatively converted it into the simple bis-olefin cage compound [1-(1-C7H7)-12-(C5H3-3,4- (CH3)2)-C2B10H10] (6). Finally, thermal treatment of 6 in refluxing toluene was employed to prepare the isomerized cycloheptatriene compound [1-(4-C7H7)-12-(C5H3-3,4- (CH3)2)-C2B10H10] (7) in high yield. These compounds represent the first metal-free cyclopentadiene and bis-olefin large cluster species reported in which the C5 ring is attached directly to the cage. The complete characterization of products by multinuclear NMR (1H, 11B, and 13C), infrared, UV-visible, and mass spectroscopic analyses is presented. The X-ray crystal structures of 3 and 7 are also reported. X-ray data for 3: triclinic system, space group P1̄ with cell constants a = 6.6807(3) Å, b = 10.2939(3) Å, c = 10.3962(4) Å, a = 89.342(2)°, β = 74.610(2)°, γ = 83.373(2)°, Z = 2, R1 = 0.0487 (wR2 (all data) = 0.1272). X-ray data for 7: monoclinic system, space group P21/c with cell constants a = 7.7207(7) Å, b = 15.8730(14) Å, c = 15.5493(13) Å, β = 99.146(2)° Z = 4, R1 = 0.0761 (wR2 (all data) = 0.2050).

Original languageEnglish (US)
Pages (from-to)3381-3388
Number of pages8
JournalInorganic Chemistry
Issue number14
StatePublished - Jul 2 2001


ASJC Scopus subject areas

  • Inorganic Chemistry

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