An unexpected reaction leading to the synthesis and characterization of two Cr-N2 complexes supported by cyclic phosphorus macrocycles that contain pendant amine bases. Reactivity with acid produced hydrazine and ammonia, illustrating the first example of N2 reduction by a "Chatt-type" chromium dinitrogen complex. Computational analysis examined the initial N2 protonation steps, highlighting the thermodynamically preferred Cr products involved in N2 reduction. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.
Revised: August 26, 2013 |
Published: August 7, 2013
Citation
Mock M.T., S. Chen, M.J. O'Hagan, R.J. Rousseau, W.G. Dougherty, W.S. Kassel, and R.M. Bullock. 2013.Dinitrogen Reduction by a Chromium(0) Complex Supported by a 16-membered Phosphorus Macrocycle.Journal of the American Chemical Society 135, no. 31:11493-11496.PNNL-SA-95191.doi:10.1021/ja405668u