15875-25-9Relevant academic research and scientific papers
FTIR studies of the CH3CN-BF3 complex in solid Ar, N2, and Xe: Matrix effects on vibrational spectra
Hattori, Ryuichi,Suzuki, Eiichi,Shimizu, Kenji
, p. 123 - 134 (2005)
FTIR spectra of the four isotopically substituted 1:1 complexes of acetonitrile and boron trifluoride were recorded in Ar, N2 and Xe matrices. In Ar, previously unreported three vibrational modes of the complex were clearly observed. Several si
Synthesis of Skeletally Labeled 3-Methylhexaborane(12) and 2-Methylpentaborane(9): 10B and 11B NMR Spectral Studies of Base-Catalyzed Intramolecular Rearrangements in 2-Methylpentaborane(9)
Gaines, Donald F.,Coons, Darrell E.
, p. 3266 - 3271 (1985)
Selectively 10B labeled 3-MeB6H11 has been synthesized from 1-MeB5H8 and 96percent 10B labeled B2H6 by modification of a previously published procedure.Positions B(1), B(2), and B(6) of the labeled 3-MeB6H11 each contain 46 +/- 5percent 10B while B(3), B(4), and B(5) are isotropically normal (19percent 10B).Reaction of this compound with dimethyl ether produces 2-MeB5H8 which is 10B enriched at B(4) (47 +/- 5percent 10B) and, to a lesser extent, at B(3,5) (30 +/- 5percent 10B).In the presence of 2,6-lutidine the 10B label in the 2-MeB5H8 equilibrates into all boron positions except the methyl-substituted B(2).These are the first direct observations of the movement of cluster boron atoms in the isomerization of pentaborane(9) derivatives.Several proposed isomerization mechanisms are examined in light of these results.
Matrix isolation FTIR and DFT studies of methyl isocyanide-boron trifluoride complex
Hattori, Ryuichi,Suzuki, Eiichi,Shimizu, Kenji
, p. 165 - 170 (2005)
The FTIR spectra of CH3NC and BF3 as well as their isotopomers co-deposited in low temperature Ar matrices were recorded. We observed several new infrared bands absent in the spectra of each component. These bands were assigned to the 1:1 EDA complex of CH3NC and BF 3 based on the DFT calculations at the B3LYP/6-311++G** level. The vibrational assignments and frequencies of the observed bands are the NC stretching at 2319.9 cm-1, the BF3 degenerate stretching at 1203.8 cm-1, the BF3 symmetric stretching at 840.4 cm-1 and the BF3 symmetric deformation at 638.0 cm-1 for the CH3NC-11BF3 isotopomer. Although the BF3 symmetric stretching is infrared inactive for free BF3 of D3h symmetry, complexation with methyl isocyanide would have induced a structural change in the BF3 moiety and the activation of this mode. Apart from some numerical discrepancies, the observed frequency shifts on complexation were in good agreement with the results of DFT calculation. Therefore, the structure of CH3NC-BF3 in solid Ar would be similar to the optimized C3v geometry, which corresponds to the gas phase structure.
Reaction of Halogens with Laser-Ablated Boron. Infrared Spectra of BXn (X = F, Cl, Br, I; n = 1, 2, 3) in Solid Argon
Hassanzadeh, Parviz,Andrews, Lester
, p. 4910 - 4915 (1993)
BXn (X = F, Cl, Br, I; n = 1, 2, 3) species were produced by the reaction of laser-ablated atomic boron with F2, Cl2, Br2, and I2, trapped in solid argon at 12 +/- 1 K, and characterized by infrared absorption spectroscopy.The relative band intensities observed for BX , BX2, and BX3 species depended on the method of production.Enclosing the boron target inside a tube and codepositing boron atoms with halogen molecules enhanced the primary reaction products BX and BX2, whereas passing the halogen through the tube and coaxially mixing with atomic boron promoted the final reaction product BX3.Very low laser power favored the BX and BX2 radicals over the BX3 molecules.These studies provide further chemical evidence for the intermediate BX2 radicals.
Quantum-chemical calculations and IR spectra of the (F2)MF 2 molecules (M = B, Al, Ga, In, Tl) in solid matrices: A new class of very high electron affinity neutral molecules
Wang, Xuefeng,Andrews, Lester
, p. 3768 - 3771 (2011/04/26)
Electron-deficient group 13 metals react with F2 to give the compounds MF2 (M = B, Al, Ga, In, Tl), which combine with F 2 to form a new class of very high electron affinity neutral molecules, (F2)MF2, in solid argon and neon. These (F 2)MF2 fluorine metal difluoride molecules were identified through matrix IR spectra containing new antisymmetric and symmetric M-F stretching modes. The assignments were confirmed through close comparisons with frequency calculations using DFT methods, which were calibrated against the MF3 molecules observed in all of the spectra. Electron affinities calculated at the CCSD(T) level fall between 7.0 and 7.8 eV, which are in the range of the highest known electron affinities.
Thermal isomerization of regiospecifically 10B-labeled icosahedral carboranes
Edvenson, Gary M.,Gaines, Donald F.
, p. 1210 - 1216 (2008/10/08)
Thermal treatment of regiospecifically 10B-enriched (96%) 3-(10B)-1-2-C2nB9H12 and 2-(10B)-1,-7-C2nB9H12 (nB = boron with normal isotopic abundances) followed by 10B and 11B NMR analysis reveal that (1) 3-(10B)-1,2-C2nB9H12 undergoes rearrangements that completely scramble the enriched boron atom, (2) these rearrangements occur at a rate faster than the conversion of 1,2-C2B10H12 to 1,7-C2B10H12, (3) the 1,7-C2B10H12 that is formed does not re-form 1,2-C2B10H12 at a detectable rate, and (4) at temperatures at which 1,2-C2B10H12 forms 1,7-C2B10H12 at a significant rate, the latter undergoes no further rearrangements. The movement of 10B at 350°C in 1,2-C2B10H12 is compared to the movement predicted by various isomerization mechanisms. The mechanism that appears to give the closest agreement involves a 12-vertex nido intermediate. It was found that a number of previously considered mechanisms, including simple exchange between two boron sites, triangular face rotation in an icosahedron, diamond-square-diamond twist, and rotation of pentagonal pyramids, are extensions of the nido intermediate mechanism. The synthesis and thermal rearrangement of 3-F-S-(10B)-1-2-C2nB9H11 demonstrate that independent intramolecular fluorine migration does not occur during rearrangement.
