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Published April 14, 2004 | Supplemental Material
Journal Article Open

Hydrogenolysis of [PhBP_3]Fe≡N-p-tolyl:  Probing the Reactivity of an Iron Imide with H_2

Abstract

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.

Additional Information

© 2004 American Chemical Society. Received December 3, 2003. Publication Date (Web): March 23, 2004. We thank the NSF (CHE-01232216) and the DOE (PECASE) for financial support. The authors acknowledge David M. Jenkins and Larry M. Henling for technical assistance.

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Supplemental Material - ja0399122si20040306_051359.pdf

Supplemental Material - ja0399122si20040306_051507.cif

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August 19, 2023
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