Intermediates in the oxidation of azide ion in acidic solutions

1986 ◽  
Vol 90 (6) ◽  
pp. 1198-1203 ◽  
Author(s):  
Zeev B. Alfassi ◽  
W. A. Pruetz ◽  
Robert H. Schuler
Keyword(s):  
Acidic Solutions ◽  
Azide Ion

Kinetic stabilizing effect of the 4-N-methylacetamido substituent on the phenylnitrenium ion

2001 ◽  
Vol 79 (12) ◽  
pp. 1875-1880 ◽  
Author(s):  
Patrick H Ruane ◽  
Robert A McClelland
Keyword(s):  
Positive Charge ◽  
Flash Photolysis ◽  
Ph Profile ◽  
Phenyl Azide ◽  
Acidic Solutions ◽  
Nitrenium Ion ◽  
Azide Ion ◽  
Methoxy Substituent ◽  
Long Lifetime ◽  
Arylnitrenium Ions

Photolysis of 4-(N-methylacetamido)phenyl azide in aqueous solution results in quantitative formation of the 4-(N-methylacetamido)phenylnitrenium ion, this cation arising from solvent protonation of an initially formed singlet arylnitrene. The cation is observed by flash photolysis, and is identified through characteristic quenching by azide ion and by 2'-deoxyguanosine, both excellent nucleophiles for arylnitrenium ions in water. The nitrenium ion is protonated in acidic solutions to form the 4-(N-methylacetamido)aniline dication, whose pKa is determined to be 1.5 based on the rate–pH profile. This means that the nitrenium ion is relatively basic, which suggests that there is significant positive charge on the N-methylacetamido group. Further evidence for this is seen in the remarkably long lifetime (5 ms) of the nitrenium ion in water. In fact, the 4-(N-methylacetamido)phenylnitrenium ion is 5000-fold longer-lived than the 4-methoxy-substituted analog. A 4-methoxy substituent on a phenyl ring is more electron donating according to σ+ values (–0.78 for MeO vs. –0.60 for NMeAc). The dramatic reversal in the arylnitrenium ions is another example of the failure of these to follow the carbocation scale.Key words: nitrenium ion, flash photolysis, amide substituent.

ChemInform Abstract: Intermediates in the Oxidation of Azide Ion in Acidic Solutions.

1986 ◽  
Vol 17 (23) ◽  
Author(s):  
Z. B. ALFASSI ◽  
W. A. PRUETZ ◽  
R. H. SCHULER
Keyword(s):  
Acidic Solutions ◽  
Azide Ion

Electrodeposition of CoMo and CoMoP alloys from the weakly acidic solutions

2010 ◽  
Vol 46 (5) ◽  
pp. 406-415 ◽  
Author(s):  
H. Cesiulis ◽  
N. Tsyntsaru ◽  
A. Budreika ◽  
N. Skridaila
Keyword(s):  
Acidic Solutions

Effect of sulfosalicylic acid (C7H6O6S) on the electrodeposition of pure ZnS nanocrystal thin films from acidic solutions

2013 ◽  
Vol 87 ◽  
pp. 511-517 ◽  
Author(s):  
Xinhua Xu ◽  
Feng Wang ◽  
Zhilin Li ◽  
Jingjun Liu ◽  
Jing Ji ◽  
...  
Keyword(s):  
Thin Films ◽  
Sulfosalicylic Acid ◽  
Acidic Solutions
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