21107-45-9Relevant academic research and scientific papers
An experimental solution to the missing hydrogens question surrounding the macropolyhedral 19-vertex boron hydride monoanion [B 19H22]-, a simplification of its synthesis, and its use as an intermediate in the first example of syn -B18H 22 to anti -B18H22 isomer conversion
Londesborough, Michael G. S.,Bould, Jonathan,Base, Tomas,Hnyk, Drahomir,Bakardjiev, Mario,Holub, Josef,CisaRova, Ivana,Kennedy, John D.
, p. 4092 - 4098 (2010/07/04)
The macropolyhedral [B19H22]- monoanion 1 and the dianion [B19H21]2- 2 are synthesized in consistent 86-92% yields by the reaction of [PSH]+[syn-B 18H21]- with BH3(SMe2) in 1,2-Cl2C2H4 at 72 °C. [PS is an abbreviation for Proton Sponge, 1,8-bis-(dimethylamino)naphthalene. PSH is its protonated derivative.] The molecular structures of 1 and 2 were elucidated as their [PS{BH2}]+ and [PS{BH2}]2 + salts 1a and 2a by single-crystal X-ray diffraction studies, in which all atoms were located, and supported by mass spectrometric analyses together with calculations of the cluster molecular geometries (ab ignitio and/or DFT) and of 11B chemical shifts based on GIAO-DFT shielding tensors. Acidification of dianion 2 with CF3COOH in acetonitrile, H2SO4 in dichloromethane, or aqueous HCl results in the clean formation of the monoanion [B19H22]- 1. Conversely, shaking a concentrated acetonitrile solution of 1 in 0.5 M aqueous NaOH cleanly yields the [B19H21]2- dianion 2. Reaction of a dichloromethane solution of 1 with a 36% aqueous solution of HCHO in the presence of H2SO4 quantitatively converts 1 at room temperature to a 1:1 mixture of the syn- and anti-isomers of B 18H22. This cluster dismantling process is the first example of a syn- to anti-B18H22 isomer conversion.
Metal-Promoted Fusion and Linkage of B5H81-, 1-XB5H71-, (X = D, CH3), B10H131-, and (ε5-C5H5)CoB4H71-. Facile Routes to B10H14 and (η5-C5H5)2Co2B8H10 Isomers.
Brewer, Cynthia T.,Grimes, Russell N.
, p. 3552 - 3558 (2007/10/02)
This study examined the conversions, via oxidative fusion or coupling, of B5H81- to B10H14 and 2,2'-(B5H8)2 in the presence of FeCl2/FeCl3, of B5H81- to B10H14 alone in the presence of RuCl3, and of 1-XB5H71- (X = D and CH3) to 2,4-B10H12D2 and 2,2-(1-CH3B5H7)2 with RuCl3 or FeCl2/FeCl3.The B10H131- ion was shown to form n- and i-B18H22 on treatment with RuCl3 in THF and subsequent exposure to air.The RuCl3-promoted fusions of the square-pyramidal cobaltaboranes 2-(ε5-C5H5)CoB4H71- and 1-(ε5-C5H5)CoB4H71- (both analogues of B5H81- to give nido-(η-C5H5)2Co2B8H12 isomers were also studied.The 2-isomer yields primarily 5,8-, 1,5-, and 1,7-(η-C5H5)2Co2B8H12, while the 1-isomer affords only 2,4-(η5-C5H5)2Co2B8H12.All these observations support a fusion mechanism in which two square-pyramidal substrate molecules, facilitated by coordination to a common metal ion, are initially joined at their basal edges and then complete the fusion process to give a nido 10-vertex cage in which the original apex (1-vertex) atoms become the 2,4-vertexes in the product.The new compounds were characterized via infrared, 11B and 1H NMR, mass spectra, and in some cases by two-dimensional (2D) 11B homonuclear NMR.
