Annihilation of aromatic cation radicals by ion-pair and radical pair collapse. Unusual solvent and salt effects in the competition for aromatic substitution

1987 ◽  
Vol 109 (25) ◽  
pp. 7824-7838 ◽  
Author(s):  
S. Sankararaman ◽  
W. A. Haney ◽  
J. K. Kochi
Keyword(s):  
Radical Pair ◽  
Ion Pair ◽  
Aromatic Substitution ◽  
Salt Effects ◽  
Cation Radicals

Transformations of Ferric Chloride-Generated Stilbene Cation Radicals. The Effect of Aromatic Substitution and a Comparison with Anodic Oxidation

2015 ◽  
Vol 10 (10) ◽  
pp. 2207-2220 ◽  
Author(s):  
Fong-Jiao Hong ◽  
Kam-Weng Chong ◽  
Yun-Yee Low ◽  
Noel F. Thomas ◽  
Toh-Seok Kam
Keyword(s):  
Anodic Oxidation ◽  
Ferric Chloride ◽  
Aromatic Substitution ◽  
Cation Radicals

Photochemistry of rhodamine dye salts involving intra-ion-pair electron transfer

2003 ◽  
Vol 81 (6) ◽  
pp. 789-798 ◽  
Author(s):  
Guilford Jones II ◽  
Xiaochun Wang ◽  
Jingqiu Hu
Keyword(s):  
Electron Transfer ◽  
Ethyl Acetate ◽  
Rhodamine 6G ◽  
Radical Pair ◽  
Ion Pairs ◽  
Ion Pair ◽  
Thiocyanate Ion ◽  
Rhodamine Dye ◽  
Triplet Radical Pair ◽  
Pair State

The electron-transfer photochemistry of rhodamine 6G thiocyanate ion pairs has been investigated. For dye in a low polarity solvent, such as ethyl acetate, the emission of rhodamine 6G is significantly quenched by thiocyanate counterions. Laser photolysis of rhodamine 6G and thiocyanate in ethyl acetate was studied in detail with the identification of the reduced rhodamine 6G radical species (λmax = 410 nm). The growth and decay of the R6G radical could be accounted for in part by a mechanism involving initial formation of dye triplet followed by electron transfer which provides a triplet radical-pair state on a µs timescale.Key words: electron transfer, ion pair, rhodamine 6G, triplet state.

Kinetic evidence for the importance of solvent-separated ion pairs during the solvolyses of adamantylideneadamantyl derivatives

2004 ◽  
Vol 82 (9) ◽  
pp. 1336-1340
Author(s):  
Xicai Huang ◽  
Andrew J Bennet
Keyword(s):  
Ionic Strength ◽  
Transition State ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Kinetic Isotope Effects ◽  
Ion Pair ◽  
Salt Effects ◽  
Kinetic Isotope

The aqueous ethanolysis reactions of adamantylideneadamantyl tosylate, -bromide, and -iodide (1-OTs, 1-Br and 1-I) were monitored as a function of ionic strength. Special salt effects are observed during the solvolyses of both homoallylic halides, but not in the case of the tosylate 1-OTs. The measured α-secondary deuterium kinetic isotope effects for the solvolysis of 1-Br in 80:20 and 60:40 v/v ethanol–water mixtures at 25 °C are 1.110 ± 0.018 and 1.146 ± 0.009, respectively. The above results are consistent with the homoallylic halides reacting via a virtual transition state in which both formation and dissociation of a solvent-separated ion pair are partially rate-determining. While the corresponding transition state for adamantylideneadamantyl tosylate involves formation of the solvent-separated ion pair.Key words: salt effects, kinetic isotope effect, internal return, solvolysis, ion pairs.

Time-resolved ESR study on photochemical formation of radical pair in cyclodextrin cavities

1991 ◽  
Vol 69 (11) ◽  
pp. 1643-1648 ◽  
Author(s):  
Hisao Murai ◽  
Yoshinori Yamamoto ◽  
Yasumasa J. I'Haya
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Spin Polarization ◽  
Room Temperature ◽  
Radical Pair ◽  
Ion Pair ◽  
Time Resolved ◽  
Excited Triplet ◽  
Photochemical Formation ◽  
Fixed Orientation

The photoreduction of xanthone with diethylaniline in cyclodextrin cavities was studied at 77 K and room temperature by a time-resolved ESR technique. The radical pair observed in β- and γ-cyclodextrins showed inverted spin polarization compared to that of precursor excited triplet xanthone. This result is rationalized by taking account of the fixed orientation of the radical ion pair in the cyclodextrins. Frozen aqueous solutions and dried powder-like samples provided similar results. The spectrum of the radical pair was also detected in an aqueous solution of β-cyclodextrin at room temperature. Key words: cyclodextrins, xanthone, spin polarization, radical ion-pair, time-resolved ESR.

scholarly journals The photochemistry of 1-naphthylmethyl carbonates and carbamates

1994 ◽  
Vol 72 (5) ◽  
pp. 1254-1261 ◽  
Author(s):  
T. Parman ◽  
J.A. Pincock ◽  
P.J. Wedge
Keyword(s):  
Electron Transfer ◽  
Singlet State ◽  
Radical Pair ◽  
Ion Pair ◽  
Excited Singlet State ◽  
Excited Singlet ◽  
Homolytic Cleavage ◽  
Product Yields ◽  
Oxygen Bond

The photochemistry in methanol of 1-naphthylmethyl phenyl carbonate (3) and 1-naphthylmethyl benzyl carbonate (4) has been studied. Products resulting from both the 1-naphthylmethyl cation and the 1-naphthylmethyl radical are obtained for 3, but only from the cation for 4. Similar results were obtained for the corresponding 1-naphthylmethyl derivatives 5 and 6 of N-phenyl and N-benzyl carbamic acids. The product yields for all four compounds can be explained by a mechanism of initial homolytic cleavage of the 1-naphthylmethyl carbon–oxygen bond from the excited singlet state. The radical pair generated then partitions between the two pathways: electron transfer to form the ion pair or decarboxylation. For PhO-CO-O• and PhNH-CO-O•, decarboxylation is rapid and competitive with electron transfer. For PhCH2O-CO-O• and PhCH2NH-CO-O•, decarboxylation is slower, electron transfer dominates, and only products from the ion pair are obtained.

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