Abstract
The kinetics of the substitution reaction between [OsN(H 2O)(CN) 4] − and N 3 − showed that the nitrido ligand with its strong σ- and π-electron donor ability labilizes the osmium(VI) complex. The metaloxygen bond strength decreases due to the large trans influence of the nitrido ligand, which allows substitution reactions with N 3 − at a rate of 1.89(7)M − s −1 at 25°C. [OsN(H 2O)(CN) 4] − is a much weaker acid (P K a1 = 7.49) compared to [OsO(H 2O)(CN) 4], as a result of the larger trans influence of N 3− compared to O 2−. A linear free energy relationship exists between the p K a1-values and the substitution rates for different [ML(H 2O)(CN) 4] n− complexes (M = Mo IV, W IV, Re V and Os VI; L = O 2− and N 3−).
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