Substituent effects on silene reactivity — Reactive silenes from photolysis of phenylated tri- and tetrasilanes

2008 ◽  
Vol 86 (12) ◽  
pp. 1105-1117 ◽  
Author(s):  
William J Leigh ◽  
Andrey G Moiseev ◽  
Eugenie Coulais ◽  
Farahnaz Lollmahomed ◽  
Mohammad S Askari
Keyword(s):  
Phenyl Ring ◽  
Kinetic Data ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Substituent Effects ◽  
Laser Flash ◽  
Acetonitrile Solution ◽  
Ortho Position ◽  
Absolute Rate ◽  
Reported Data

Laser flash photolysis of 2-phenylheptamethyltrisilane (5d), 2,2-diphenylhexamethyltrisilane (5e), and phenyltris(trimethylsilyl)silane (5f) in hexane and acetonitrile solution affords strong, long-lived transient absorptions centered in the 440–470 nm range, which are assigned to the transient silenes formed via [1,3]-trimethylsilyl migration into the ortho-position of a phenyl ring on the basis of their UV–vis spectra and kinetic data for their reactions with methanol (MeOH), acetic acid (AcOH), acetone, 2,3-dimethyl-1,3-butadiene (DMB), carbon tetrachloride (CCl4), and oxygen. The silene derivatives are formed along with the corresponding silylenes (SiMePh, SiPh2, and Si(SiMe3)Ph, respectively) upon photolysis of these compounds in solution, and indeed, weak, short-lived transient absorptions assignable to the silylenes can also be detected in laser photolysis experiments with the three compounds in hexane, superimposed on the much more prominent absorptions due to the silenes. The silylene absorptions are quenched by MeOH and triethylsilane (Et3SiH) with absolute rate constants varying over the narrow ranges of (1.1–1.8) × 1010 (mol/L)–1 s–1 and (2.5–3.6) × 109 (mol/L)–1 s–1, respectively, in excellent agreement with previously reported values for SiPh2 and SiMe2 under the same conditions. The kinetic data obtained for the silenes are compared to previously reported data for the reactions of the same substrates with the related silenes (6a–6c) formed by photolysis of pentamethylphenyl-, 1,1,1,2-tetramethyl-2,2-diphenyl-, and 1,1,1-trimethyl-2,2,2-triphenyldisilane (5a–5c, respectively) under similar conditions. The comparison provides the first systematic, quantitative assessment of the stabilizing effects of trialkylsilyl substitution at the silenic silicon atom in silene derivatives.Key words: silene, silylene, trisilane, tetrasilane, kinetics.

Laser flash photolysis determination of absolute rate constants for reactions of bromine atoms in solution

1993 ◽  
Vol 115 (18) ◽  
pp. 8340-8344 ◽  
Author(s):  
J. C. Scaiano ◽  
M. Barra ◽  
M. Krzywinski ◽  
R. Sinta ◽  
G. Calabrese
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Absolute Rate

scholarly journals Measurements of Rate Constants for HO2 + NO and NH2 + NO Reactions by Time-Resolved Photoionization Mass Spectrometry

1995 ◽  
Vol 16 (1) ◽  
pp. 43-51 ◽  
Author(s):  
Takashi Imamura ◽  
Nobuaki Washida
Keyword(s):  
Mass Spectrometry ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Absolute Rate ◽  
Time Resolved ◽  
Photoionization Mass Spectrometry

Absolute rate constants for HO2 + NO and NH2 + NO reactions were measured by a photoionization mass spectrometry coupled with a laser flash photolysis. HO2 and NH2 radicals were photoionized by an Ar resonance lamp and were detected as their parent ions (HO2+ and NH2+). The rate constants were determined to be K(HO2 + NO)=(6.5  ± 2.0) 10−12cm3molecule−1s−1K(NH2 + NO)=(1.9  ± 0.3) 10−11cm3molecule−1s−1 Both rates are consistent with those previously reported.

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.

Competing photodehydration and excited-state intramolecular proton transfer (ESIPT) in adamantyl derivatives of 2-phenylphenols

2011 ◽  
Vol 89 (2) ◽  
pp. 221-234 ◽  
Author(s):  
Nikola Basarić ◽  
Nikola Cindro ◽  
Yunyan Hou ◽  
Ivana Žabčić ◽  
Kata Mlinarić-Majerski ◽  
...  
Keyword(s):  
Excited State ◽  
Carbon Atom ◽  
Proton Transfer ◽  
Phenyl Ring ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Intramolecular Proton Transfer ◽  
Hydroxyl Group ◽  
Quantum Yields

2-Phenylphenol derivatives strategically substituted with a hydroxyadamantyl substituent were synthesized and their photochemical reactivity was investigated. Derivatives 9 and 10 undergo competitive excited-state intramolecular proton transfer (ESIPT) from the phenol to the carbon atom of the adjacent phenyl ring and formal ESPT from the phenol to the hydroxyl group coupled with dehydration. These two processes (both via S1) give rise to two classes of quinone methides (QMs) that revert to starting material or react with nucleophiles, respectively. ESIPT to carbon atoms was studied by performing photolyses in the presence of D2O, whereupon deuterium incorporation to the adjacent phenyl ring was observed ([Formula: see text] = 0.1–0.2). The competing formal ESPT and dehydration takes place with quantum yields that are an order of magnitude lower and was studied by isolation of photomethanolysis products. Derivative 8 did not undergo ESIPT to carbon atom. Owing to the presence of an intramolecular H bond, an efficient ESIPT from the phenol to the hydroxyl group coupled with dehydration gives a QM that efficiently undergoes electrocyclization (overall [Formula: see text] = 0.33), to give chroman 16. In addition, spiro[adamantane-2,9′-(4′-hydroxy)fluorene] (12) undergoes ESIPT, unlike the previously reported unreactive parent 2-hydroxyfluorene. The reactive singlet excited states of the prepared biphenyl and fluorene molecules were characterized by fluorescence spectroscopy, whereas laser flash photolysis (LFP) was performed to characterize the longer lived QM intermediates.

Fast kinetics studies of the Lewis acid–base complexation of transient stannylenes with σ- and π-donors in solution

2018 ◽  
Vol 20 (31) ◽  
pp. 20555-20570 ◽  
Author(s):  
Ian R. Duffy ◽  
William J. Leigh
Keyword(s):  
Lewis Acid ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Acid Base ◽  
Dft Methods ◽  
Fast Kinetics ◽  
Kinetics Studies ◽  
Reported Data

The complexation of SnMe2 and SnPh2 with a variety of σ- and π-donors and its effects on their dimerization reactions has been studied by laser flash photolysis and DFT methods, and compared to reported data for the Si and Ge homologues.

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