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The Mechanism of N–N Double Bond Cleavage by an Iron(II) Hydride Complex

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b04654· OSTI ID:1467439
 [1];  [2];  [3];  [4];  [5];  [6];  [7]
  1. Univ. of Rochester, NY (United States). Dept. of Chemistry; Department of Chemistry, University of Rochester, Rochester, NY 14627
  2. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  3. Univ. of Rochester, NY (United States). Dept. of Chemistry; Rani Channamma Univ., Vidyasangama, Belagavi (India)
  4. Univ. of Rochester, NY (United States). Dept. of Chemistry
  5. Max Planck Inst. for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
  6. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry and CASCaM
  7. Univ. of Rochester, NY (United States). Dept. of Chemistry; Yale Univ., New Haven, CT (United States). Dept. of Chemistry
+ Show Author Affiliations

The use of hydride species for substrate reductions avoids strong reductants, and may enable nitrogenase to reduce multiple bonds without unreasonably low redox potentials. Here in this work, we explore the N=N bond cleaving ability of a high-spin iron(II) hydride dimer with concomitant release of H2. Specifically, this diiron(II) reacts with azobenzene (PhN=NPh) to perform the fourelectron reduction to two imido groups, where two electrons come from H2 reductive elimination and the other two come from iron oxidation. The rate law of the H2 releasing reaction indicates that diazene binding occurs prior to H2 elimination, and the negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation is the rate-limiting step. Thus, substrate binding causes reductive elimination of H2 that formally reduces the metals, and the metals use the additional two electrons to cleave the N-N multiple bond.

Research Organization:
Univ. of North Texas, Denton, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15387
OSTI ID:
1467439
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 138; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Density Functional Calculations for Prediction of 57 Fe Mössbauer Isomer Shifts and Quadrupole Splittings in β-Diketiminate Complexes journal June 2017
Direct amidation of esters with nitroarenes journal March 2017
Synthesis of Chromium(II) Complexes with Chelating Bis(alkoxide) Ligand and Their Reactions with Organoazides and Diazoalkanes journal January 2020
Nitrogen Reduction to Ammonia on a Biomimetic Mononuclear Iron Centre: Insights into the Nitrogenase Enzyme journal December 2017
Reactivity of hydride bridges in a high-spin [Fe 3 (μ-H) 3 ] 3+ cluster: reversible H 2 /CO exchange and Fe–H/B–F bond metathesis journal January 2017
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A model for dinitrogen binding in the E 4 state of nitrogenase journal January 2019

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