2875-95-8Relevant academic research and scientific papers
Unprecedented double nucleophilic addition of a hydride at a central carbon of an η3-allyl ligand
Minato, Makoto,Sekimizu, Ryoko,Uchida, Daisuke,Ito, Takashi
, p. 3695 - 3698 (2004)
Treatment of η3-allyl compound [Cp 2Mo(η3-C3H5)]+ (1; Cp = η5-C5H5) with MH (M = Li, Na) resulted in reduction of the allyl ligand to give propane. Deuterium-labeling studies were used to trace the origins and fates of the hydrogen atoms. The mechanism is discussed in light of the HSAB principle. The studies showed that the formation of propane can be explained by 1,2-hydrogen migration from the central to the terminal carbon of the allyl ligand, and the subsequent double nucleophilic addition of the hydride at the central carbon.
Low-Temperature Decomposition of Alkyl Iodides on Ni(100) Surfaces: Evidence for the Formation of Alkyl Free Radicals
Zaera, Francisco,Tjandra, Sariwan
, p. 3044 - 3049 (2007/10/02)
Previous studies have shown that alkyl iodides dissociate on metal substrates around 200 K to produce iodine atoms alkyl moieties on the surface; here we report a new low-temperature decomposition pathway for those compounds on Ni(100) that leads to the formation of a close to 1:1 alkane-alkene mixture below 150 K.This latter reactions is proposed to occur via a mechanism where alkyl iodide dissociation results in the direct formation of free radicals.A combination of thermal desorption experiments with isotope labeling and hydrogen coadsorption was used to establish the importance of the nickel surface in the overall process and to rule out either surface disproportionation or gas-phase reactions as the source of the low-temperature products.Evidence was also obtained for a possible rearrangement of the adsorbed alkyl iodide molecules from a fat geometry into an upright configuration at high coverages, a change that would explain the ease with which the radicals formed after C-I bond scission are released into the gas phase instead of being left on the surface as adsorbed alkyl surface moieties.A comparison with other systems is also presented.
