Iron-molybdenum cofactor of nitrogenase: electrochemical determination of the electron stoichiometry of the oxidized/semi-reduced couple.

The number of electrons involved in the more positive of the two redox couples of the iron-molybdenum cofactor of Azotobacter vinelandii nitrogenase has been investigated by controlled potential coulometry in both the oxidizing and reducing directions. A n value of 1 was determined for interconversion of the oxidized and semi-reduced states of the cofactor. This electron count was confirmed by double integration of the S = 3/2 electron paramagnetic resonance signal exhibited by the semi-reduced state.