<oai_dc:dc xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:oai_dc="http://www.openarchives.org/OAI/2.0/oai_dc/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xsi:schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd">
  <dc:creator>Piech, Krzysztof</dc:creator>
  <dc:creator>Bally, Thomas</dc:creator>
  <dc:creator>Sikora, Adam</dc:creator>
  <dc:creator>Marcinek, Andrzej</dc:creator>
  <dc:date>2007-03-01</dc:date>
  <dc:description xmlns:ns0="xml" ns0:lang="en">A new method for investigating the mechanisms of nitric oxide release from NO donors under oxidative and reductive conditions is presented. Based on the fragmentation of &lt;i&gt;N&lt;/i&gt;-nitrosoamines, it allows generation and spectroscopic characterization of nitrenium cations, amide anions, and aminyl radicals. X-irradiation of &lt;i&gt;N&lt;/i&gt;-nitroso-&lt;i&gt;N&lt;/i&gt;,&lt;i&gt;N&lt;/i&gt;-diphenylamine &lt;b&gt;1&lt;/b&gt; in Ar matrices at 10 K is found to yield the corresponding radical ions, which apparently undergo spontaneous loss of NO&lt;sup&gt;°&lt;/sup&gt; under the conditions of this experiment (&lt;b&gt;1&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt;⁺ seems to survive partially intact, but not &lt;b&gt;1&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt;&lt;b&gt;&lt;/b&gt;⁻). One-electron reduction or oxidation of &lt;b&gt;1&lt;/b&gt; is observed upon doping of the Ar matrix with DABCO, an efficient hole scavenger, or CH₂Cl₂, an electron scavenger, respectively. The resulting diphenylnitrenium cation, &lt;b&gt;2&lt;/b&gt;⁺, and the diphenylamide anion, &lt;b&gt;2&lt;/b&gt;⁻, were characterized by their full UV-vis and mid-IR spectra. The best spectra of &lt;b&gt;2&lt;/b&gt;⁺ and &lt;b&gt;2&lt;/b&gt;⁻ were obtained if &lt;b&gt;1&lt;/b&gt; was homolytically photodissociated to diphenylaminyl radical &lt;b&gt;2&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt; and NO&lt;sup&gt;°&lt;/sup&gt; prior to ionization. &lt;b&gt;2&lt;/b&gt;&lt;b&gt;⁺&lt;/b&gt; and &lt;b&gt;2&lt;/b&gt;⁻ are bleached on irradiation at &lt;340 nm to form &lt;b&gt;2&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt; or, in part, &lt;b&gt;1&lt;/b&gt;. DFT and CCSD quantum chemical calculations predict that the dissociation of &lt;b&gt;1&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt;⁺ and &lt;b&gt;1&lt;/b&gt;&lt;sup&gt;°&lt;/sup&gt;&lt;b&gt;&lt;/b&gt;⁻ is slightly endothermic, a tendency which is partially reversed if one allows for complexation of the resulting &lt;b&gt;2&lt;/b&gt;⁺ (and, presumably, &lt;b&gt;2&lt;/b&gt;⁻) with NO&lt;sup&gt;°&lt;/sup&gt;. The method described in this work should prove generally applicable to the generation and study of nitrenium cations and amide anions R₂N&lt;sup&gt;+/-&lt;/sup&gt; under matrix and ambient conditions (i.e., in solution).</dc:description>
  <dc:format>application/pdf</dc:format>
  <dc:identifier>https://folia.unifr.ch/global/documents/300543</dc:identifier>
  <dc:identifier>https://folia.unifr.ch/documents/300543/files/bally_mao.pdf</dc:identifier>
  <dc:language>eng</dc:language>
  <dc:relation>info:eu-repo/semantics/altIdentifier/doi/10.1021/ja066855e</dc:relation>
  <dc:rights>info:eu-repo/semantics/openAccess</dc:rights>
  <dc:rights>License undefined</dc:rights>
  <dc:source>Journal of the American Chemical Society. - 2007, vol. 129, no. 11, p. 3211 -3217</dc:source>
  <dc:subject>info:eu-repo/classification/udc/54</dc:subject>
  <dc:title xmlns:ns1="xml" ns1:lang="en">Mechanistic aspects of the oxidative and reductive fragmentation of n-nitrosoamines: a new method for generating nitrenium cations, amide anions, and aminyl radicals</dc:title>
  <dc:type>http://purl.org/coar/resource_type/c_6501</dc:type>
</oai_dc:dc>