Abstract
The complex, trans-[Mo(N 2 2(Ph 2PCH 2CH 2PPH 2)] +, decomposes with the loss of both N 2 ligands in tetrahydrofuran-methanol (26% V/V)0.1N LiX electrolyte (X = Cl − and ClO 4su−) via a first order dissociative mechanism. The rate constant of decomposition at 25° C in the presence of lithium chloride is 2.4± 0.2 × 10 −1 s −1 and the activation parameters are: E a = 24 +- 2 Kcal mol −1 and ΔS * = +19 ± 5 cal deg −1 mol l−1. The kinetic parameters for the perchlorate electrolyte are similar. The molybdenum-containing product of decomposition disproportionates to produce Mo(O) and Mo(II) species which further react, in some cases, with the anions of the electrolyte. All reactions are initiated and monitored by electrochemical techniques.
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