Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

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

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

Publisher URL: http://dx.doi.org/10.1021/jacs.7b04552

DOI: 10.1021/jacs.7b04552

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.