31277-24-4Relevant academic research and scientific papers
Thermochemistry of Silaethylene and Methylsilylene from Experiment and Theory
Shin, Seung Koo,Irikura, Karl K.,Beauchamp, J. L.,Goddard, William A.
, p. 24 - 30 (2007/10/02)
Fourier transform ion cyclotron resonance spectroscopy has been used to examine the deprotonation energetics of the methylsilyl cation, CH3SiD2+, to yield silaethylene and methylsilylene proton affinities of 205 +/- 3 and 215 +/- 4 kcal/mol, respectively.These values combined with the known heat of formation of methylsilyl cation, yield ΔHof 298(CH2SiH2) = 43 +/- 3 kcal/mol and ΔHof 298(CH3SiH) = 53 +/- 4 kcal/mol.These results are corroborated by ab initio generalized valence bond-configuration interaction calculations which indicate that silaethylene is more stable than methylsilylene by 11.6 kcal/mol, in excellent agreement with the experimental difference (10 +/- 3 kcal/mol).The adiabatic ionization potential of methylsilylene is calculated to be 8.22 eV, which is lower than the value of 8.85 eV determined for silaethyene using photoelectron spectroscopy.
Hydrogen Abstraction from Amines: Formation of Aminyl vs. α-Aminoalkyl Radicals
Nazran, A. S.,Griller, D.
, p. 1970 - 1971 (2007/10/02)
A series of electron paramagnetic experiments were carried out which showed that dialkylaminyl radicals do not readily attack dialkylamines to form α-aminoalkyl radicals.These results disprove earlier conclusions that such processes were the major pathways for formation of α-aminoalkyl radicals in free radical reactions involving dialkylamines.By contrast, tert-butoxyl radicals were found to efficiently abstract hydrogen from amines.Rate constants for C-H and N-H abstraction by tert-butoxyl were respectively 6.5 x 107 and 1.1 x 107 for Me2NH, 6.6 x 107 and 1.0 x 107 for Et2NH, 1.3 x 107 and 3 x 106 for n-PrNH2, 7 x 106 and 3 x 106 for n-BuNH2, and 3.3 x 106 for t-BuNH2 (units M-1 s-1).
