1975
DOI: 10.1039/p29750000675
|View full text |Cite
|
Sign up to set email alerts
|

Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals

Abstract: The oxidation of simple aliphatic sulphides [MeSMe, EtSEt, (CH,),S] by hydroxyl radicals occurs via a complex reaction mechanism. The first step is addition of the OH* to sulphur to form R2SOH radicals. At low sulphide concentrations ( < ~O -* M ) R,SOH rapidly eliminates H 2 0 to form a RSR(-H)* radical which may be described by the mesomeric forms -CH-S-and -CH=S-.This radical is ultimately also formed at higher sulphide concentrations but via a different pathway. R2SOH increasingly reacts with another R2S m… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1
1

Citation Types

4
138
0
1

Year Published

1976
1976
2017
2017

Publication Types

Select...
7
2

Relationship

0
9

Authors

Journals

citations
Cited by 144 publications
(143 citation statements)
references
References 0 publications
4
138
0
1
Order By: Relevance
“…This lack of BP d-formation is likely due to the fast proton transfer within a solvent cage, yielding the BP radical. This proton is presumably donated by the quencher molecule, yielding the relatively stable C-centered radical [18], which could not be observed in the flash photolysis due to its inconvenient absorption overlap with the BP ground state. Despite of those difficulties, the supporting evidence for the proposed reaction mechanism came from the steady-state irradiation experiments, where the product of recombination of the BP ketyl radical and a C-centered radical of N-Ac-Met-OCH 3 (formed upon deprotonation of the initially formed S-centered radical cation) was detected and identified by means of HPLC-MS analysis.…”
Section: Resultsmentioning
confidence: 98%
“…This lack of BP d-formation is likely due to the fast proton transfer within a solvent cage, yielding the BP radical. This proton is presumably donated by the quencher molecule, yielding the relatively stable C-centered radical [18], which could not be observed in the flash photolysis due to its inconvenient absorption overlap with the BP ground state. Despite of those difficulties, the supporting evidence for the proposed reaction mechanism came from the steady-state irradiation experiments, where the product of recombination of the BP ketyl radical and a C-centered radical of N-Ac-Met-OCH 3 (formed upon deprotonation of the initially formed S-centered radical cation) was detected and identified by means of HPLC-MS analysis.…”
Section: Resultsmentioning
confidence: 98%
“…Above all, much of the late Dieter Asmus' seminalw ork [4][5][6][7][8][9][10][11][12][13] has apparently been forgotten, [72] but also the pioneering experimental studies of Meot-Ner, [19] Pauling [3] and Hiberty's [29] rationalization of oddelectron bond energiesi nt erms of valence-bond theory and Bock [34] and Nelsen's [35] fundamental studies on three-electron p-bonds are apparently no longerp resenti no ur general picture of bondingt heory.T his short review attempts to remind us of these classical examples of physicalo rganic chemistry, which taken on an even more importantr ole as the importance of radicals and radical ions is increasingly recognized in both biology and photovoltaics and whose importance in transition-metal chemistry has recently been reviewed. [73] Computational Section All calculations used the Gaussian 09 series of programs.…”
Section: Discussionmentioning
confidence: 99%
“…Theoretical interest in odd-electron bonding was strengthened by Asmus' observation of intramolecular SÀS three-electron bonds in solution. [4] This was followed by similar studies on S-halogen three-electron bonds [5][6][7][8][9] and acyclic SÀS three-electron bonded radical cations. [10,11] Furthert hree-electron bonds of sulfur with nitrogen, oxygen [12] and phosphorus [13] and between two nitrogen [14,15] and two iodine [16] centers [17] werea lso reported.…”
Section: Introductionmentioning
confidence: 99%
“…This conclusion is also in agreement with our previous finding that the complexed radical cation (RzS)2.+ is rather stable and reactions essentially occurred through the uncomplexed R2S.+. 24 Further support for this mechanism arises from the corre-5.3 X loW3, 3.6 X sponding results from N20 saturated solutions containing di-tert-butyl thioether M). In contrast to the other thioethers no complexed radical cations are formed (probably due to steric reasons)24 and the monomer radical cation is immediately available for the reaction M) and diethyl disulfide…”
Section: Oxidation By Brzs- Another Powerful Oxidant Is Br2mentioning
confidence: 88%