Benzylic Cations with Triplet Ground States:  Computational Studies of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, and Oxenium Ions Substituted with Meta π Donors

2007 ◽  
Vol 129 (33) ◽  
pp. 10113-10119 ◽  
Author(s):  
Arthur H. Winter ◽  
Daniel E. Falvey ◽  
Christopher J. Cramer ◽  
Benjamin F. Gherman
Keyword(s):  
Ground States ◽  
Computational Studies ◽  
Nitrenium Ions ◽  
Carbenium Ions

Structures of Reactive Nitrenium Ions:  Time-Resolved Infrared Laser Flash Photolysis and Computational Studies of SubstitutedN-Methyl-N-arylnitrenium Ions

2000 ◽  
Vol 122 (34) ◽  
pp. 8271-8278 ◽  
Author(s):  
Sanjay Srivastava ◽  
Patrick H. Ruane ◽  
John P. Toscano ◽  
Michael B. Sullivan ◽  
Christopher J. Cramer ◽  
...  
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Infrared Laser ◽  
Computational Studies ◽  
Time Resolved ◽  
Nitrenium Ions ◽  
Arylnitrenium Ions

1997 Alfred Bader Award Lecture Reactivities of arylnitrenium ions with guanine derivatives and other nucleophiles

1998 ◽  
Vol 76 (10) ◽  
pp. 1327-1337 ◽  
Author(s):  
Robert A McClelland ◽  
Timothy A Gadosy ◽  
Daniel Ren
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Lone Pair ◽  
Primary Amines ◽  
Diffusion Limit ◽  
Nitrenium Ions ◽  
Carbenium Ions ◽  
Alkyl Amines ◽  
Guanine Derivatives ◽  
Arylnitrenium Ions

The carcinogens 4-aminobiphenyl and 2-aminofluorene are metabolized to hydroxylamine esters that undergo N-O heterolysis to produce arylnitrenium ions that react with DNA, especially at guanine residues. These nitrenium ions and a number of their derivatives have been studied by the laser flash photolysis technique, to provide direct kinetic information about the lifetimes of the electrophiles in water and their reactivities with added nucleophiles. Arylnitrenium ions ArNH+ are longer-lived in water than arylcarbenium analogs ArCH2+, in some cases significantly longer-lived. The nitrenium ions do react with azide ion at the diffusion limit (providing the cation is not highly stabilized). This behaviour completely parallels that of carbenium ions. The biphenylyl- and fluorenylnitrenium ions react with guanine derivatives such as 2-deoxyguanosine (dG) with rate constants that are close to or at the diffusion limit (2 × 109 M-1 s-1) for the more reactive cations. Thus, in spite of cation lifetimes of the order of 100 ns to a millisecond in water, dG effectively competes with the solvent. The product is a C8 adduct, the same adduct observed with carcinogenic arylamines and DNA. With delocalized carbenium ions that have similar lifetimes, guanine derivatives compete very poorly with water. Thus, arylnitrenium ions have high dG:water selectivities; arylcarbenium ions have low selectivities. Nitrenium ions and carbenium ions do have parallel reactivities with primary alkyl amines. More reactive cations show a greater reactivity with less basic amines and the rate constants level below the diffusion limit. This can be explained by hydrogen bonding of the amine lone pair. Using the NH2 group of the alkyl amines as a model for the C2-NH2 group of guanine shows why nitrenium ions show no detectable reactivity at this site. The rate constant for the nitrenium-guanine reaction that forms the C8 adduct is at least an order of magnitude greater than that of a nitrenium-NH2 reaction. Nitrenium ions do form a guanine-NH2 adduct in DNA, suggesting that incorporation into the polymer changes reactivity patterns. With imidazoles, nitrenium ions show reactivity trends that parallel the nitrenium-dG reaction, with rate constants levelling at the 2 × 109 limit for the more reactive cations. Imidazole itself and 1-methylimidazole are generally less reactive than dG, while 2-methylimidazole and 1,2-dimethylimidazole are very similar. A Brönsted-like plot incorporating points for dG, primary amines and imidazoles shows no correlation of nitrenium rate constants with nitrogen basicity. This is true even if only dG and imidazoles are considered. Thus a previous correlation of nitrenium reactivity with purine N7 basicity is suspect. The conclusion is that there is some feature of guanine that makes its reaction with nitrenium ions unusually fast. The reasons for this are not immediately apparent, especially since there is conflicting evidence as to the detailed nature of the mechanism of the reaction that forms the C8 adduct. Key words: nitrenium, aryl azide, guanine, DNA, carcinogen.

Computational Studies of Human Motion: Part 1, Tracking and Motion Synthesis

2005 ◽  
Author(s):  
David A. Forsyth ◽  
Okan Arikan ◽  
Leslie Ikemoto ◽  
James O'Brien ◽  
Deva Ramanan
Keyword(s):  
Human Motion ◽  
Computational Studies ◽  
Motion Synthesis
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