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Mechanistic Studies on the Oxidation of Hydrazine by Tris(biguanide)manganese(IV) in Aqueous Acidic Media

✍ Scribed by Basab Bijayi Dhar; Ritam Mukherjee; Subrata Mukhopadhyay; Rupendranath Banerjee

Publisher
John Wiley and Sons
Year
2005
Tongue
German
Weight
90 KB
Volume
88
Category
Article
ISSN
0018-019X

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✦ Synopsis

The title Mn IV complex, [Mn(LH 2 ) 3 ] 4 (LH 2 biguanide H 2 NC( NH)NHC( NH)NH 2 ), an authentic two-electron oxidant, quantitatively oxidizes hydrazine (H 2 NNH 2 ) to dinitrogen in the pH interval 2.00 ± 3.50. The net four-electron oxidation of hydrazine is provided by two Mn IV as established by stoichiometric studies. The overall reaction is composed of two parallel paths:

The values of k 1 and k 2 (in m À1 s À1 ) are, respectively, (5.50 AE 0.6) ¥ 10 À3 and 11.4 AE 1.5 at 25.08 and I 1.0m (NaNO 3 ). The order k 2 ) k 1 is unusual as protonated oxidants are generally more reactive than their conjugate bases. The remarkably superior reactivity of the conjugate base of the oxidant in oxidizing N 2 H 5 may be at least in part due to an overall positive-charge reduction in [Mn(LH 2 ) 2 (LH)] 3 as compared to [Mn(LH 2 ) 3 ] 4 that favors reaction with positively charged N 2 H 5 , and more plausibly, a change in the mechanism is responsible for this result as not k 1 but k 2 is substantially lowered in D 2 O media indicating that proton motion is coupled with electron transfer in the k 2 path. The rate-determining step appears to be a one-electron transfer from N 2 H 5 to Mn IV .

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