Hydrogenolysis of [PhBP3]Fe≡N-p-tolyl: Probing the Reactivity of an Iron Imide with H2

Article abstract of DOI:10.1021/ja0399122

This paper describes the reductive hydrogenolysis of a low-spin (S = 1/2) iron(III) imide. Pseudotetrahedral [PhBP₃]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, [PhBP₃]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, [PhBP₃]Fe(η⁵-cyclohexadienyl), which has also been independently prepared and structurally characterized. Evidence is presented to suggest that the final [PhBP₃]Fe(η⁵-cyclohexadienyl) product is formed via benzene insertion into a reactive [PhBP₃]Fe^II-H intermediate. Copyright