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The MoFe7S9C1– unit of the nitrogenase cofactor (FeMoco) attracts chemists and biochemists due to its unusual ability to bind aerial dinitrogen (N2) at ambient condition and catalytically convert i...

The syntheses of the two novel complexes [Ag{Mo/W(CO)6}2]+[F‐{Al(ORF)3}2]− (RF=C(CF3)3) are reported along with their structural and spectroscopic characterization. The X‐ray structure shows that three carbonyl ligands from each M(CO)6 fragment bend towards the silver atom within binding Ag−C distance range. DFT calculations of the free cations [Ag{M(CO)6}2]+ (M=Cr, Mo, W) in the electronic singlet state give equilibrium structures with C 2 symmetry with two bridging carbonyl groups from each hexacarbonyl ligand. Similar structures with C 2 symmetry (M=Nb) and D 2 symmetry (M=V, Ta) are calculated for the isoelectronic group 5 anions [Ag{M(CO)6}2]− (M=V, Nb, Ta). The electronic structure of the cations is analyzed with the QTAIM and EDA‐NOCV methods, which provide detailed information about the nature of the chemical bonds between Ag+ and the {M(CO)6}2 q (q = −2, M = V, Nb, Ta; q = 0, M = Cr, Mo, W) ligands., Hexacarbonyls as ligands: The molecules M(CO)6 (M=Mo, W) act as ligands towards the silver ion, giving the title compounds [Ag{M(CO)6}2]+[F‐{Al(ORF)3}2]− (RF=C(CF3)3). Their structures and bonding have been analyzed and compared with those of the very recently prepared isoelectronic complexes [Ag{M(CO)6}2]− (M=Nb, Ta).