Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe

Demyan E. Prokopchuk, Eric Wiedner, Eric D. Walter, Codrina V. Popescu, Nicholas A. Piro, W. Scott Kassel, R Morris Bullock, Michael T. Mock

Research output: Contribution to journalArticle

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Abstract

The geometric constraints imposed by a tetradentate P4N2 ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe0(N2)(P4N2) complex catalyzes the conversion of N2 to N(SiR3)3 (R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N2 silylation catalyst to date (up to 65 equiv N(SiMe3)3 per Fe center). Elevated N2 pressures (>1 atm) have a dramatic effect on catalysis, increasing N2 solubility and the thermodynamic N2 binding affinity at Fe0(N2)(P4N2). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N2 binding. In addition, X-ray crystallography, 57Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe0, FeI, and FeII complexes reveals that the free energy of N2 binding across three oxidation states spans more than 37 kcal mol-1.

Original languageEnglish
Pages (from-to)9291-9301
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number27
DOIs
Publication statusPublished - Jul 12 2017

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Thermodynamics
Spectrum Analysis
Spectroscopy
Oxidation
X ray crystallography
Electrochemistry
Ultraviolet spectroscopy
Catalysis
Free energy
Paramagnetic resonance
Pressure
Temperature
Solubility
Metals
X Ray Crystallography
Ligands
Catalysts

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Prokopchuk, D. E., Wiedner, E., Walter, E. D., Popescu, C. V., Piro, N. A., Kassel, W. S., ... Mock, M. T. (2017). Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe. Journal of the American Chemical Society, 139(27), 9291-9301. https://doi.org/10.1021/jacs.7b04552

Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe. / Prokopchuk, Demyan E.; Wiedner, Eric; Walter, Eric D.; Popescu, Codrina V.; Piro, Nicholas A.; Kassel, W. Scott; Bullock, R Morris; Mock, Michael T.

In: Journal of the American Chemical Society, Vol. 139, No. 27, 12.07.2017, p. 9291-9301.

Research output: Contribution to journalArticle

Prokopchuk, Demyan E. ; Wiedner, Eric ; Walter, Eric D. ; Popescu, Codrina V. ; Piro, Nicholas A. ; Kassel, W. Scott ; Bullock, R Morris ; Mock, Michael T. / Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 27. pp. 9291-9301.
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