ja7b01982_si_002.cif (12.06 MB)

Testing the Push–Pull Hypothesis: Lewis Acid Augmented N2 Activation at Iron

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posted on 17.04.2017 by Jacob B. Geri, James P. Shanahan, Nathaniel K. Szymczak
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.