Submitted by jag4016 on September 24, 2021 - 1:42pm
| Title | Testing the Push-Pull Hypothesis: Lewis Acid Augmented N2 Activation at Iron. |
| Publication Type | Journal Article |
| Year of Publication | 2017 |
| Authors | Geri JB, Shanahan JP, Szymczak NK |
| Journal | J Am Chem Soc |
| Volume | 139 |
| Issue | 16 |
| Pagination | 5952-5956 |
| Date Published | 2017 04 26 |
| ISSN | 1520-5126 |
| Keywords | Boranes, Electrochemical Techniques, Electrons, Iron Compounds, Lewis Acids, Molecular Conformation, Nitrogen |
| Abstract | We present a systematic investigation of the structural and electronic changes that occur in an Fe(0)-N2 unit (Fe(depe)2(N2); depe = 1,2-bis(diethylphosphino)ethane) upon the addition of exogenous Lewis acids. Addition of neutral boranes, alkali metal cations, and an Fe2+ complex increases the N-N bond activation (Δ νNN up to 172 cm-1), decreases the Fe(0)-N2 redox potential, polarizes the N-N bond, and enables -N protonation at uncommonly anodic potentials. These effects were rationalized using combined experimental and theoretical studies. |
| DOI | 10.1021/jacs.7b01982 |
| Alternate Journal | J Am Chem Soc |
| PubMed ID | 28414226 |
| PubMed Central ID | PMC5965694 |
| Grant List | R01 GM111486 / GM / NIGMS NIH HHS / United States |