The effect of leaving radical on the formation of tetrahydroselenophene by SHi ring closure: an experimental and computational study

2015 ◽  
Vol 13 (8) ◽  
pp. 2310-2316 ◽  
Author(s):  
Amber N. Hancock ◽  
Sofia Lobachevsky ◽  
Naomi L. Haworth ◽  
Michelle L. Coote ◽  
Carl H. Schiesser
Keyword(s):  
Kinetic Parameters ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Computational Study ◽  
Kinetic Studies ◽  
Laser Flash ◽  
Ring Closure ◽  
Computational Techniques ◽  
High Level

Competition kinetic studies augmented with laser-flash photolysis and high-level computational techniques [G3(MP2)-RAD], with [COSMO-RS, SMD] and without solvent correction, provide kinetic parameters for the ring closures of a series of 4-(alkylseleno)butyl radicals.

scholarly journals Kinetic studies of C1 and C2 Criegee intermediates with SO2 using laser flash photolysis coupled with photoionization mass spectrometry and time resolved UV absorption spectroscopy

2018 ◽  
Vol 20 (34) ◽  
pp. 22218-22227 ◽  
Author(s):  
N. U. M. Howes ◽  
Z. S. Mir ◽  
M. A. Blitz ◽  
S. Hardman ◽  
T. R. Lewis ◽  
...  
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Kinetic Studies ◽  
Laser Flash ◽  
Major Product ◽  
Time Resolved ◽  
Photoionization Mass Spectrometry ◽  
Criegee Intermediates ◽  
Wide Range ◽  
Kinetics Of

Kinetics of CH2OO + SO2 confirmed over a wide range of [SO2]. Acetaldehyde observed as a major product of the reaction of CH3CHOO + SO2.

Direct detection of methylphenylgermylene and 1,2-dimethyl-1,2-diphenyldigermene — Kinetic studies of their reactivities in solution

2006 ◽  
Vol 84 (7) ◽  
pp. 934-948 ◽  
Author(s):  
William J Leigh ◽  
Ileana G Dumbrava ◽  
Farahnaz Lollmahomed
Keyword(s):  
Acetic Acid ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Direct Detection ◽  
Kinetic Studies ◽  
Laser Flash ◽  
Absolute Rate ◽  
Hydrocarbon Solvents ◽  
Diffusion Controlled

Photolysis of 1,3,4-trimethyl-1-phenylgermacyclopent-3-ene (5) in hydrocarbon solvents containing isoprene, methanol, or acetic acid affords 2,3-dimethyl-1,3-butadiene (DMB) and the expected trapping products of methyl phenylgermylene (GeMePh) in chemical yields exceeding 90%. The germylene has been detected in hexane solution by laser flash photolysis as a short-lived species (τ ~ 2 µs) exhibiting a UV-vis absorption spectrum centered at λmax = 490 nm. It decays with second-order kinetics and a rate constant close to the diffusion-controlled limit, with the concomitant growth of a second longer-lived transient (λmax = 420 nm) that is assigned to a mixture of (E)- and (Z)-1,2-dimethyl-1,2-diphenyldigermene (4). Absolute rate constants have been determined for the reactions of the germylene with primary and tertiary amines (n-BuNH2 and Et3N, respectively), acetic acid (AcOH), a terminal alkyne and alkene, isoprene, DMB, CCl4, and the group 14 hydrides Et3SiH and Bu3SnH. GeMePh is slightly more reactive than GePh2 towards all the reagents studied in this work; both are significantly less reactive than GeMe2 toward the same substrates. Absolute rate constants for the reactions of 4 have also been measured or assigned upper limits in every case and are compared to previously reported values for tetraphenyl- and tetramethyl-digermene with the same reagents.Key words: germylene, digermene, kinetics, laser flash photolysis, germirane, germirene, vinylgermirane, complex, UV–vis spectrum, insertion, addition.

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