7175-75-9Relevant academic research and scientific papers
Channeling of products in the hot atom reaction H + (CN)2 → HCN/HNC + CN and in the reaction of CN with CH3SH
Decker, Brian K.,Macdonald, R. Glen
, p. 6817 - 6825 (2007/10/03)
Infrared transient absorption spectroscopy was used to determine the total product branching fractions for the gas-phase hot atom reaction H + (CN)2 → HCN/HNC + CN (a) and the reaction CN + CH3SH → HCN/HNC + CH3S/CH2SH (b) at 293 K. The reactive H atoms had an initial mean translational energy of 92 kJ mol-1, with a 38 kJ mol-1 fwhm Gaussian energy distribution. The branching fractions determined for the product channels forming HCN and HNC, respectively, are 0.88 and 0.12 (±0.05) for reaction (a) and 0.81 and 0.19 (±0.08) for reaction (b). The bimolecular rate constant for reaction (b) was measured to be (2.7 ± 0.3) × 10-10 cm3 molec-1 s-1 at 293 K. The observed product branching fractions for reaction (a) are consistent with the assumption that the average reactive cross sections for the two product channels are approximately equal above their respective energy thresholds. The results for reaction (a) are compared with the related H + XCN (X = Br, Cl) reactions. The large rate coefficient for reaction (b) suggests an interaction via a long-range intermolecular potential, which is facilitated by the small ionization energy of CH3SH and large electron affinity of CN. The results for reaction (b) are compared with the related reactions of Cl and OH with CH3SH.
Gas-Phase Reactions of Fe(1-) and Co(1-) with Simple Thiols, Sulfides, and Disulfides by Fourier Transform Mass Spectrometry
Sallans, L.,Lane, K. R.,Freiser, B. S.
, p. 865 - 873 (2007/10/02)
Fe(1-) and Co(1-) are found to react with simple thiols, sulfides, and disulfides.The primary reaction products formed from these metal anions, M(1-), and thiols include MS(1-), MSH(1-), and MSH2(1-) and suggest a mechanism involving initial insertion of the metal into the weak C-S bond.Similarly, C-S insertion is the main mode of attack in the reactions with the sulfides and disulfides, in analogy to what is observed for the reaction of metal cations.Collision-induced dissociation is used to support the proposed structures for the primary products, H-Fe(1-)-SH andFe(1-)-SH.Some of the thermochemical data derived from this study include D0(M(1-)-S)>103 kcal/mol and D0(M(1-)-SH)=83 +/- 9 kcal/mol.Finally, a brief survey of the reactivity of V(1-), Cr(1-), and Mo(1-) with selected organosulfur compounds is also reported.
SCAVENGING OF RADICALS FROM THE GAS PHASE BY FREEZING WITH DIMETHYL DISULFIDE: 1. TEST OF THE METHOD FOR LIGHT RADICALS.
Schottler,Homann
, p. 688 - 694 (2007/10/02)
H and O atoms and methyl radicals produced in microwave discharges of H//2/He, O//2/He and CH//4/He mixtures, respectively, were scavenged by supersonic nozzle probing with subsequent freezing and reaction with dimethyl disulfide on a liquid nitrogen cooled wall. The main reaction products for the three kinds of radicals were CH//3SH, CH//3S(O)SCH//3 and CH//3SCH//3, respectively. The scavenging efficiencies for the different radicals were determined and measured as a function of the gas phase radical concentration, the flow of scavenger molecules, the pressure in the vacuum chamber, and the conditions of the discharge and the flow through the sampling nozzle. It is concluded that this method is suitable for light radicals with reservations in the case of H atoms and can probably be used with still better success for heavier radicals.
Reactions of Triplet Carbenes with Sulfides and Disulfides: Ylide vs. Radical Formation
Alberti, A.,Griller, D.,Nazran, A. S.,Pedulli, G. F.
, p. 3024 - 3028 (2007/10/02)
The reactions between triplet diphenylcarbene and fluorenylidene with a variety of sulfides and disulfides were investigated with use of electron paramagnetic resonance (EPR) spectroscopy, laser flash photolysis, and product studies.Diphenylcarbene reacted with these substrates by a radical-like displacement mechanism.Rate constants were ca. 1E6 M-1 s-1, and the resulting thio-substituted diphenylmethyl radicals were identified by their EPR and optical spectra.By contrast, the analogous reactions of fluorenylidene had rate constants of 1E8-1E9 M-1 s-1 and proceeded by an ylide mechanism.Product studies were consistent with these results but were not sufficient in themselves to reveal these mechanistic differences.
