title: Hydrogenolysis of [PhBP3]Fe[triple bond]N-p-tolyl: probing the reactivity of an iron imide with H2.
abstract: This paper describes the reductive hydrogenolysis of a low-spin (S = 1/2) iron(III) imide. Pseudotetrahedral [PhBP3]FeIIIN-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(eta5-cyclohexadienyl), which has also been independently prepared and structurally characterized. Evidence is presented to suggest that the final [PhBP3]Fe(eta5-cyclohexadienyl) product is formed via benzene insertion into a reactive [PhBP3]FeII-H intermediate.
authors.affiliation: Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Steven D
authors.initials: SD
authors.lastname: Brown
authors.forename: Jonas C
authors.initials: JC
authors.lastname: Peters