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<p><span style="font-size: x-small;">Kinetics and mechanistic studies for the oxidation of N</span><span style="font-size: x-small;"><span style="font-size: xx-small;">-Benzylhydroxylamine by a Co</span><sup style="font-size: x-small;">III</sup><span style="font-size: xx-small;">-bound bridging superoxo complex in perchloric acid medium</span></span></p>

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Title Statement <p><span style="font-size: x-small;">Kinetics and mechanistic studies for the oxidation of N</span><span style="font-size: x-small;"><span style="font-size: xx-small;">-Benzylhydroxylamine by a Co</span><sup style="font-size: x-small;">III</sup><span style="font-size: xx-small;">-bound bridging superoxo complex in perchloric acid medium</span></span></p>
 
Added Entry - Uncontrolled Name GAIN, SEKHAR ; RKM VIDYAMANDIRA
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Uncontrolled Index Term Inorganic reaction mechanisms
Keywords: N-benzylhydroxylamine, Superoxo, Kinetics, Mechanisms, Oxidation- Reduction.
 
Summary, etc. <p>In aqueous perchloric acid medium (pH = 0.522 – 1.3) , N–benzylhydroxylamine ( two electron reductant)  reduces the  one electron oxidant,  superoxo ligand in [(dien)(en)Co<sup>III</sup>(O<sub>2</sub>)Co<sup>III</sup>(en)(dien)](ClO<sub>4</sub>)<sub>5</sub> (<strong>1</strong>) to the corresponding hydroperoxo complex, [(en)(dien)Co<sup>III</sup>(HO<sub>2</sub>)Co<sup>III</sup>(en)(dien)]<sup>5+</sup> (<strong>2</strong>) and itself gets oxidised to PhCH<sub>2</sub>NO  following both  proton coupled electron transfer (PCET) path and an electron – transfer (ET) reaction. The kinetics, stoichiometry and reaction mechanism clearly indicate that oxidation of PhCH<sub>2</sub>NHOH occurs through the formation of an intermediate, benzyl derivative of  aminoxyl radical (PhCH<sub>2</sub>NHO<sup>•</sup>). In the presence of excess PhCH<sub>2</sub>NHOH over <strong>1</strong>, the reaction obeys first-order kinetics and rate of the reaction increases with [PhCH<sub>2</sub>NHOH]. The reaction rate, however, decreases with increase in [H<sup>+</sup>] and the plot of 1/<em>k<sub>o</sub></em> with [H<sup>+</sup>] is linear with a small but noteworthy intercept. It is also remarked that the reaction rate remarkably decreases with increasing proportion of D<sub>2</sub>O replacing H<sub>2</sub>O in the solvent. Therefore, an H-atom transfer (HAT) from PhCH<sub>2</sub>NHOH to the bridging superoxide in <strong>1</strong> seems reasonable at the rate determining step.</p><p><strong> </strong></p>
 
Publication, Distribution, Etc. Indian Journal of Chemistry -Section A (IJCA)
2021-09-22 10:50:13
 
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http://op.niscair.res.in/index.php/IJCA/article/view/46223
 
Data Source Entry Indian Journal of Chemistry -Section A (IJCA); ##issue.vol## 60, ##issue.no## 7 (2021): INDIAN JOURNAL OF CHEMISTRY- SECTION A
 
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Nonspecific Relationship Entry http://op.niscair.res.in/index.php/IJCA/article/download/46223/465548397
http://op.niscair.res.in/index.php/IJCA/article/download/46223/465548399
http://op.niscair.res.in/index.php/IJCA/article/download/46223/465548496
 
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