Ur. Choudhury et al., Kinetics and mechanism of hydrazine oxidation by an oxo-bridged tetramanganese(IV) complex in weakly acidic media, J CHEM S DA, (4), 2000, pp. 589-592
Citations number
32
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The complex [Mn-4(mu-O)(6)(bipy)(6)](4+) 1 (bipy=2,2'-bipyridine) quantitat
ively oxidised N2H5+ to N-2. With an excess of N2H5+ the reaction proceeds
through two parallel first-order paths. In one, 1 reacts with N2H5+ and the
rate is independent of [H+] and the concentration of bipy. In the other pa
th, the rate decreases with increasing concentration of ligand and [H+]. In
this second path [Mn-4(mu-O)(6)(bipy)(5)(H2O)(N2H4)](4+) appears to be the
reactive species. The overall first-order rate constant k(0) decreases lin
early with increased mole % of D2O and k(0) in 98% D2O is substantially (3.
89 times) less than that in 0% D2O. Transfer of one electron and one proton
in the rate determining step is proposed for both the paths.