Iron(iv) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N₂

Abstract

High-valent iron alkyl complexes are rare, as they are prone to Fe–C bond homolysis. Here, we describe an unusual way to access formally iron(IV) alkyl complexes through double silylation of...

Monomethylation and -protonation of Lutetium Dinitrogen Complex

“…Significant achievements have been made in the activation and transformation of dinitrogen via transition metal (TM)–dinitrogen complexes over the past century. − Due to the unique electronic structures, rare earth (RE) dinitrogen complexes can exhibit reactivity different from the main group − and transition metals. − In contrast with the even-electron reduction (TM-(N 2 ) n − , n = 2, 4, 6) in transition metal dinitrogen complex, the odd-electron reduction species (N 2 ) 3– has been confirmed in rare earth dinitrogen complex by William Evans and colleagues since 2009. − Further EPR investigation and DFT calculations confirmed the radical property of (N 2 ) 3– . These features may relate to the restricted valencies of rare earth metal centers and the polarization of the RE–N bond. ,, In comparison with the rich reactivity of TM-(N 2 ) comlexes, − only two examples of (N 2 ) 3– functionalization have been reported. Reaction of {[(Me 3 Si) 2 N] 2 (THF)­RE} 2 ­(μ 2 -η 2 :η 2 -N 2 ) (RE = Y, Gd) with [Et 3 NH]­[BPh 4 ] led to the biprotonated ((N 2 H 2 ) 2– ) products {[(Me 3 Si) 2 N] 2 ­(THF)­RE} 2 ­(μ-N 2 H 2 ) (RE = Y, Gd) .…”