Laser flash photolysis studies of the formation and reactivities of phenyl(naphthyl)methyl carbocations generated from phosphonium salt precursors

1992 ◽  
Vol 70 (6) ◽  
pp. 1784-1794 ◽  
Author(s):  
E. O. Alonso ◽  
L. J. Johnston ◽  
J. C. Scaiano ◽  
V. G. Toscano
Keyword(s):  
Rate Constants ◽  
Phosphonium Salt ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Product Formation ◽  
Quantum Yields ◽  
Back Reaction ◽  
Transient Experiments

The photolysis of several substituted phenyl(naphthyl)methyl triphenylphosphonium chlorides has been examined using a combination of laser flash photolysis experiments and product studies. Both carbocation and radical intermediates have been characterized in the transient experiments, with the relative yields depending strongly on the solvent. For example, in alcohols, acetonitrile, or aqueous solvents cation formation predominates while acetonitrile/dioxane mixtures (5–10%) are required for the observation of radicals. Quantum yields for cation formation vary from 0.79 in methanol to 0.093 in 1:4 acetonitrile/dioxane, as measured by product studies and transient experiments, respectively. The addition of perchlorate salts leads to dramatic enhancements in the cation lifetimes; the effects are particularly pronounced for acetonitrile/dioxane mixtures where the cation yields also increase by factors of 3–4. In this case the effects are attributed primarily to replacement of chloride by perchlorate in the initial ion pairs. The combined data from both solvent and perchlorate salt effects on the cation lifetimes and yields suggest that the excited state of the phosphonium salt cleaves homolytically, followed by electron transfer within the initial radical/triphenylphosphine radical cation pair to generate carbocation, as opposed to direct heterolytic cleavage. The cation yields also indicate that back reaction to regenerate starting material, as well as product formation within the initial geminate cage, occur in some solvents. The effects of solvent and added perchlorate salts on the rate constants for reaction with nucleophiles have been examined. For example, rate constants that vary by an order of magnitude have been measured for quenching by azide ion in various aqueous acetonitrile and trifluoroethanol mixtures.

Time-resolved nanosecond and picosecond absorption studies of excited-state properties of 1-thiobenzoylnaphthalene

1989 ◽  
Vol 67 (6) ◽  
pp. 967-972 ◽  
Author(s):  
R. Minto ◽  
A. Samanta ◽  
P.K. Das
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Picosecond Laser ◽  
Laser Flash ◽  
Quantum Yields ◽  
Pulse Excitation ◽  
Nanosecond Laser Pulse ◽  
Nanosecond Laser ◽  
Quenching Rate

1-Thiobenzoylnaphthalene (TBN), known for its pericyclization reaction from the lowest excited singlet state (S1), has been subjected to nanosecond and picosecond laser flash photolysis studies. The two major transients observed in the course of nanosecond laser pulse excitation are (i) the short-lived triplet characterized by two absorption maxima (400–410 and 740–750 nm) and submicrosecond intrinsic lifetimes (80–130 ns) and (ii) a relatively long-lived species (λmax = 520 nm and τ = 220–240 ns). Various triplet-related photophysical data of TBN, including self-quenching and bimolecular quenching rate constants, have been determined. The existence of a photochemical path from S1 manifests itself in low intersystem crossing quantum yields, particularly in the polar/hydrogen-bonding solvent, methanol. From the build-up of the triplet under picosecond excitation into S1 the lifetime of the latter is estimated to be ≤ 50 ps (in benzene). The fast intrinsic decay of TBN triplet is attributable to facile intra- and intermolecular photochemistry. The 520 nm transient species could not be definitively assigned, except that it is neither a triplet nor a triplet-derived product and that it arises via photochemistry from S1. Keywords: laser flash photolysis, triplet, transients, absorption maxima, lifetimes, quenching rate constants, photochemistry, 1-thiobenzoylnaphthalenes.

Singlet Mechanism for Trans → Cis Photoisomerization of Quaternary Salts of 4-Substituted 4′-Azastilbenes (R = CN, H, CH3, and OCH3) and their Quinolinium Analogues. VIII

1985 ◽  
Vol 40 (5) ◽  
pp. 525-537 ◽  
Author(s):  
H. Görner ◽  
A. Fojtik ◽  
J. Wróblewski ◽  
L. J. Currell
Keyword(s):  
Triplet State ◽  
Low Temperatures ◽  
Room Temperature ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Quantum Yields ◽  
Polar Solvents ◽  
Effects Of Temperature

The trans → cis photoisomerization of a series of substituted stilbazolium salts (At+X− , At+: trans-1-alkyl-4-[4-R-styryl]-pyridinium and -quinolinium, R = CN. H, CH3 and OCH3, X− = I and ClO4−) was studied by laser flash photolysis and steady state irradiation measurements. The quantum yields of cis ⇄ trans photoisomerization (ϕc → t and ϕt → c ) and of fluorescence of the trans isomers (ϕf) were determined in several solvents at room temperature and at low temperatures in mixtures of either 2-methyltetrahydrofuran-dichloromethane or ethanolmethanol (E-M). In polar solvents at room temperature ϕt → c is substantial ( ≧ 0.3) and ϕf is small (10−3-10−2). Competition of fluorescence and an activated step in the trans → cis pathway is indicated by the effects of temperature on ϕf and ϕt → c (activation energy: 2 - 3 kcal/mol). A transient, observed only at low temperatures (lifetime τT > 0.5 ms in E-M below -170°C), is assigned to the lowest triplet state with trans configuration. On the basis of the effects of temperature on ϕf, ϕt → c , and the triplet yield and those of quenchers on ϕf and ϕt → c , involvement of the triplet state in the twisting process at room temperature is excluded. Therefore, a singlet mechanism is suggested for the trans → cis photoisomerization of the stilbazolium salts examined. Significant reduction of ϕt → c for iodides in solvents of moderate polarity, where ion pairs are present, is accounted for by photoinduced electron transfer in competition to trans → cis photoisomerization.

Steady state and time-resolved spectroscopic studies of the photochemistry of 1-arylsilacyclobutanes and the chemistry of 1-arylsilenes

1999 ◽  
Vol 77 (5-6) ◽  
pp. 1136-1147 ◽  
Author(s):  
William J Leigh ◽  
Rabah Boukherroub ◽  
Christine J Bradaric ◽  
Christine C Cserti ◽  
Jennifer M Schmeisser
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Singlet State ◽  
Fluorescence Emission ◽  
Laser Flash ◽  
Excited Singlet State ◽  
Acetonitrile Solution ◽  
Quantum Yields ◽  
Excited Singlet

Direct photolysis of 1-phenylsilacyclobutane and 1-phenyl-, 1-(2-phenylethynyl)-, and 1-(4'-biphenylyl)-1-methylsilacyclobutane in hexane solution leads to the formation of ethylene and the corresponding 1-arylsilenes, which have been trapped by photolysis in the presence of methanol. Quantum yields for photolysis of the three methyl-substituted compounds have been determined to be 0.04, 0.26, and 0.29, respectively, using the photolysis of 1,1-diphenylsilacyclobutane Φsilene = 0.21) as the actinometer. The corresponding silenes have been detected by laser flash photolysis; they have lifetimes of several microseconds, exhibit UV absorption maxima ranging from 315 to 330 nm, and react with methanol with rate constants on the order of (2-5) × 109 M-1 s-1 in hexane. Absolute rate constants for reaction of 1-phenylsilene and 1-methyl-1-phenylsilene with water, methanol, tert-butanol, and acetic acid in acetonitrile solution have been determined, and are compared to those of 1,1-diphenylsilene under the same conditions. With the phenylethynyl- and biphenyl-substituted methylsilacyclobutanes, the triplet states can also be detected by laser flash photolysis, and are shown to not be involved in silene formation on the basis of triplet sensitization and (or) quenching experiments. Fluorescence emission spectra and singlet lifetimes have been determined for the three 1-aryl-1-methylsilacyclobutanes, 1,1-diphenylsilacyclobutane, and a series of acyclic arylmethylsilane model compounds. These data, along with the reaction quantum yields, allow estimates to be made of the rate constants for the excited singlet state reaction responsible for silene formation. 1-Methyl-1-phenylsilacyclobutane undergoes reaction from its lowest excited singlet state with a rate constant 10-80 times lower than those of the other three derivatives. The results are consistent with a stepwise mechanism for silene formation, involving a 1,4-biradicaloid intermediate that partitions between product and starting material.Key words: silene, silacyclobutane, photochemistry, biradical.

Singlet Methylene Removal Rate Constants from the (0,1,0) Vibrational Level: Enhancement via Complex-Mediated Vibrational Relaxation

2001 ◽  
Vol 215 (6) ◽  
Author(s):  
M.A. Buntine ◽  
G.J. Gutsche ◽  
W.S. Staker ◽  
M.W. Heaven ◽  
K.D. King ◽  
...  
Keyword(s):  
Vibrational Level ◽  
Rate Constants ◽  
Vibrational Relaxation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Removal Rate ◽  
Laser Flash ◽  
Laser Absorption ◽  
Photolysis Laser ◽  
Singlet Methylene

The technique of laser flash photolysis/laser absorption has been used to obtain absolute removal rate constants for singlet methylene,

Formation and nucleophilic capture of N-nitrosiminium ions

1999 ◽  
Vol 77 (5-6) ◽  
pp. 1148-1161 ◽  
Author(s):  
Latifa Chahoua ◽  
Alain Vigroux ◽  
Yvonne Chiang ◽  
James C Fishbein
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Aqueous Media ◽  
Laser Flash ◽  
Azide Ion ◽  
Iminium Ions ◽  
Nucleophilic Trapping

A study of the solvolysis of a series of (N-nitrosomethylamino)arylmethyl esters and azides and the products of nucleophilic trapping of the corresponding N-nitrosiminium ion intermediates in aqueous media, 25°C, ionic strength 1 M is reported. Structure-reactivity data for the forward and reverse reactions have been obtained. In three cases, the rate constants for reactions of the cations with nucleophiles have been measured directly by laser flash photolysis. The data allow a comparison of the degree to which the N-methyl-N-nitroso functionality enhances cation stability from a thermodynamic and kinetic perspective. It has been possible to deduce that the carbon basicity of azide ion is less than 1 kcal/mol greater than that of acetate ion.Key words: nitrosiminium ions, α-acetoxynitrosamines, carbocations, iminium ions, nucleophilicity.

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

Flash photolysis production of the tetrahedral intermediate of the methanolysis of methyl benzoate. Direct measurement of the rate of breakdown of the conjugate base form

1990 ◽  
Vol 68 (3) ◽  
pp. 375-382 ◽  
Author(s):  
Robert A. McClelland ◽  
V. M. Kanagasabapathy ◽  
Steen Steenken
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Carbonyl Oxygen ◽  
Methyl Benzoate ◽  
Ion Concentration ◽  
Hydroxide Ion ◽  
Tetrahedral Intermediate ◽  
Conjugate Base

Laser flash photolysis in aqueous basic solutions of the ortho acid derivatives 1-(phenyldimethoxymethyl)benzimidazole 2 and 4-bromo-1-(phenyldimethoxymethyl)imidazole 3 results in production of the phenyldimethoxymethyl cation, which has λmax at 260 nm. The cation decays in reactions with water (k = 9.9 × 104 s−1) and hydroxide ion (2.5 × 108 M−1 s−1) to finally yield methyl benzoate, whose formation was monitored at 234 nm. In solutions with pH 10–12, rate constants measured at this wavelength are the same as those obtained at 260 nm, but with pH > 13 and pH < 9, rate constants at 234 nm are smaller. With pH 9–10 and pH 12–13, single exponential kinetics are not observed at 234 nm. This behavior is interpreted in terms of a scheme where at each pH there are two consecutive first-order reactions, cation → phenyldimethoxyhydroxymethane (5) → ester, and the pH dependencies of the rate constants are such that they cross twice over the pH range of this study. The intermediate 5 is the tetrahedral intermediate formed in the methanolysis of methyl benzoate, and the 234-nm buildup at pH > 13 and pH < 9 directly measures its breakdown. At pH > 13 the rate constant is independent of pH with k = 9 × 106 s−1. This represents the rapid expulsion of methoxide from the conjugate base of 5. At pH < 9 the rate constants are proportional to hydroxide ion concentration, with [Formula: see text]. In these solutions the neutral intermediate predominates and the dependence on [OH−] of its rate of conversion to ester is interpreted in terms of breakdown of the anion and protonation of this species by water occurring at comparable rates. Thus, [Formula: see text] represents a situation where there is partial rate-limiting deprotonation of the neutral intermediate by hydroxide. The intermediate of this study bears a close resemblance to the tetrahedral intermediate of the hydrolysis of methyl benzoate. The observation that the anionic forms of such intermediates undergo breakdown at rates similar to those associated with the establishment of proton transfer equilibrium explains why the ester undergoes carbonyl oxygen exchange in base at a rate slower than hydrolysis. Keywords: tetrahedral intermediate, flash photolysis, ester hydrolysis.

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