Absolute rate constants for the decarbonylation of the phenylacetyl radical

Lunazzi, L.; Ingold, K. U.; Scaiano, J. C.

doi:10.1021/j100227a001

Cited by 114 publications

(74 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4) depletion of signal. The modest growth observed presumably reflects reaction [lo], and is consistent with recent rate measurements for this process in homogeneous solution (19). These processes are not unlike those reported by Turro et al (9,18), frequently in CTAC, except that our data include a substantial amount of information in the -50 ns range, which was not examined in detail in earlier reports.…”

Section: Discussionsupporting

confidence: 77%

Flash photolysis of phenylacetatopentaminecobalt(III) in aqueous solution. Generation of benzyl radicals and their reversible trapping by cupric ions in homogeneous and micellar solutions

Scaiano¹,

Leigh²,

Ferraudi³

1984

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

The photodecomposition of [Co(NH3)5OC(O)CH2C6H5](ClO4)2 is a convenient source of benzyl radicals in aqueous systems. The radicals react with cupric ions with a rate constant of (2.1 ± 0.2) × 107 M−1 s−1 to yield a complex that is formed reversibly. This complex can decay to Cu(I), but at high radical concentrations the recombination of benzyl radicals in equilibrium with it can become the predominant decay path. The reaction of benzyl radicals (from 1,3-diphenylacetone) in anionic micelles in the presence of Cu2+ leads to strong signals from the same intermediate, CuCH2C6H52+.

show abstract

Section: Discussionsupporting

confidence: 77%

Flash photolysis of phenylacetatopentaminecobalt(III) in aqueous solution. Generation of benzyl radicals and their reversible trapping by cupric ions in homogeneous and micellar solutions

Scaiano¹,

Leigh²,

Ferraudi³

1984

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…This contrasts with the situation for alkoxyl radicals where the transition states for b-scission to carbonyl products are more strongly solvated than the starting radicals. Therefore, and in contrast to alkoxyl radicals, rate constants for the a-scission of acyl radicals [33][34][35][36] and for the b-scission of peroxyl radicals 36,37 are smaller in polar and HBD solvents than in alkanes, see Scheme 9.…”

mentioning

confidence: 99%

The frequently overlooked importance of solvent in free radical syntheses

2011

Self Cite

View full text Add to dashboard Cite

“…The decarbonylation reaction is a very fast process (2, 3); the lifetime of PhCH2COS is 190 ns at 300 K in methanol (3).…”

Section: Introductionmentioning

confidence: 99%

“…On short time scales the production of the radical by two separate processes (i.e. reactions [2] and [ 3 ] ) can be easily identified (2, 3).…”

Section: Laser Jash Photolysismentioning

confidence: 99%

Photochemistry of dibenzylketone in Nafion membranes

Wintgens¹,

Scaiano²

1987

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Photolysis of dibenzyl ketone in vacuum-dried Nafion membranes leads to the detection of fluorescence from the protonated ketone and formation of modest yields of benzyl cations characterized using laser photolysis techniques. Exchange of the acid sites in Nafion by cationic surfactants leads to decreased environmental polarity and a change in mechanism towards the benzyl radical chemistry which is common in organic solvents. The decay of benzyl radicals in Nafion membranes shows magnetic field dependence which indicates that geminate processes play an important role.

show abstract

Absolute rate constants for the decarbonylation of the phenylacetyl radical

Cited by 114 publications

References 0 publications

Flash photolysis of phenylacetatopentaminecobalt(III) in aqueous solution. Generation of benzyl radicals and their reversible trapping by cupric ions in homogeneous and micellar solutions

Flash photolysis of phenylacetatopentaminecobalt(III) in aqueous solution. Generation of benzyl radicals and their reversible trapping by cupric ions in homogeneous and micellar solutions

The frequently overlooked importance of solvent in free radical syntheses

Photochemistry of dibenzylketone in Nafion membranes

Contact Info

Product

Resources

About