Dinitrogen Coordination to a High-Spin Diiron(I/II) Species.

Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber-Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high-spin metal centers; however, iron-dinitrogen coordination chemistry remains dominated by low-valent states, contrasting the enzyme systems. Here, we report a high-spin mixed-valent cis-(µ-1,2-dinitrogen)diiron(I/II) complex [(FeBr)2 (µ-N2 )Lbis ]- (2), where [Lbis ]- is a bis(ß-diketiminate) cyclophane. Field-applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S=7 /2 Fe2 N2 unit with D=-5.23 cm-1 and consequent slow magnetic relaxation.