Bio‐Inspired Iron and Nickel Complexes

Redox-Controlled and Reversible N–N Bond Forming and Splitting with an IronIV Terminal Imido Ligand

“…Second, and to establish if an intermediate with a ferrous ion, such as [ B–Fe ], was likely formed in the reduction of 2 OAc , we treated 3 with the low-coordinate Fe II precursor [Fe­{N­(SiMe 3 ) 2 } 2 ] and found complex 1 to be formed in 58% spectroscopic yield in addition to 2 equiv of HN­(SiMe 3 ) 2 after 24 h at 75 °C (Scheme and Figure S8). To further explore the ability of hydrazine ligand 3 to act as a synthon for both pincer ligand and an imido group, we examined another low-coordinate species, such as [Co­{N­(SiMe 3 ) 2 } 2 ] .…”

“…AgOAc and AgNO 3 were purchased from Fisher Scientific and used as received without any further purification. The bis(pyrroly)pyridine ligand H 2 ( tBu pyrr) 2 py (2,6-bis(3,5-di-tert-butyl-pyrrolyl)pyridine), 35 [Fe(N-(SiMe 3 ) 2 ) 2 ], 36 and [Co(N(SiMe 3 ) 2 ) 2 ], 37 as well as [{( tBu pyrr) 2 py}-FeNAd] 30 were synthesized according to previously published procedures. KC 8 was prepared as a lustrous dark golden solid by stirring oxide-free potassium chunks with 8 equiv of dry graphite at 100 °C for 6 h. NMR spectra were recorded on a Varian Inova 400 MHz.…”