This paper describes the reductive hydrogenolysis of a low-spin (S = 1/2) iron(III) imide. Pseudotetrahedral [PhBP_3]Fe^(III)≡N-p-tolyl is reduced by hydrogen at ambient temperature and pressure in benzene solution. The reduction appears to proceed in a stepwise fashion. An intermediate S = 2 iron(II) anilide, [PhBP_3]Fe(N(H)-p-tolyl), is observed and has been independently generated and structurally characterized. Prolonged hydrogenolysis in benzene results in the complete hydrogenolysis of the Fe−N linkage to release H2N-p-tolyl. The major iron-containing product formed from this step is the diamagnetic cyclohexadienyl complex, [PhBP_3]Fe(η^5-cyclohexadienyl), which has also been independently prepared and structurally characterized. Evidence is presented to suggest that the final [PhBP_3]Fe(η^5-cyclohexadienyl) product is formed via benzene insertion into a reactive [PhBP_3]Fe^(II)-H intermediate
