ENDOR Characterization of (N2)FeII(μ-H)2FeI(N2)-: A Spectroscopic Model for N2 Binding by the Di-μ-hydrido Nitrogenase Janus Intermediate

Hao Yang, Jonathan Rittle, Amy R. Marts, Jonas C. Peters*, Brian M. Hoffman

*Corresponding author for this work

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

The biomimetic diiron complex 4-(N2)2, featuring two terminally bound Fe-N2 centers bridged by two hydrides, serves as a model for two possible states along the pathway by which the enzyme nitrogenase reduces N2. One is the Janus intermediate E4(4H), which has accumulated 4[e-/H+], stored as two [Fe-H-Fe] bridging hydrides, and is activated to bind and reduce N2 through reductive elimination (RE) of the hydride ligands as H2. The second is a possible RE intermediate. 1H and 14N 35 GHz ENDOR measurements confirm that the formally Fe(II)/Fe(I) 4-(N2)2 complex exhibits a fully delocalized, Robin-Day type-III mixed valency. The two bridging hydrides exhibit a fully rhombic dipolar tensor form, T ≈ [-t, +t, 0]. The rhombic form is reproduced by a simple point-dipole model for dipolar interactions between a bridging hydride and its "anchor" Fe ions, confirming validity of this model and demonstrating that observation of a rhombic form is a convenient diagnostic signature for the identification of such core structures in biological centers such as nitrogenase. Furthermore, interpretation of the 1H measurements with the anchor model maps the g tensor onto the molecular frame, an important function of these equations for application to nitrogenase. Analysis of the hyperfine and quadrupole coupling to the bound 14N of N2 provides a reference for nitrogen-bound nitrogenase intermediates and is of chemical significance, as it gives a quantitative estimate of the amount of charge transferred between Fe and coordinated N, a key element in N2 activation for reduction.

Original languageEnglish (US)
Pages (from-to)12323-12330
Number of pages8
JournalInorganic chemistry
Volume57
Issue number19
DOIs
StatePublished - Oct 1 2018

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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