Mo/WN2 and N2H2 complexes with trans nitrile ligands: electronic structure, spectroscopic properties and relevance to nitrogen fixation

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N2 Mediated By Metal Complexes

“…[95] This work complements previous studies on reduction pathways in Mo/W N 2 , NNH, and NNH 2 complexes. DFT calculations on model systems Mo(N 2 ) 2 (dppe) 2 , MoF(NNH)(dppe) 2 and [MoF(NNH 2 )(dppe) 2 ]…”

“…The new work reports the structure of W(N 2 )(NCEt)(dppe) 2 , the first tungsten dinitrogen nitrile complex having a P 4 ligand set, along with electronic, vibrational and DFT calculations on this and related complexes. [95] In these systems, the N 2 ligand is activated to a higher degree than the corresponding bis(dinitrogen) systems, making the first protonation step more facile. Further addition of protons is more difficult because the N À NH 2 ligand is less activated; in addition, the nitrile ligand becomes labile at this stage and this prevents formation of NH 3 .…”

Vibrational Properties of [FeH(N2)(depe)2]+ and [FeCl(N2)(depe)2]+]: Dinitrogen Bonding in the Low Activation Limit

“…However, while it equally acts to lower the N-N stretching frequency, it actually diminishes the charge on the N 2 ligand and thus lowers its activation. In order to obtain deeper insight into the factors influencing the bonding and activation of N 2 , we are investigating dinitrogen complexes of transition-metals with respect to their electronic structure, their spectroscopic properties and their ability to form protonated intermediates [8,9,16,25].…”

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

“…lxviii,lxx Likewise, the only late transition metal N 2 complexes with significant N 2 2− character have π-donor β-diketiminatexxiii or P 2 N 2 supporting ligands. viii In another example, more electron-donating trans ligands in octahedral W dinitrogen complexes give more N-N weakening, lxxi and electron-withdrawing carbonyl supporting ligands shorten N-N bonds in end-on N 2 complexes. lxxii …”