Even if molybdenum is also considered, there is no series in which complexes exist for both oxidation states and contain the same alkyl substituent. Furthermore, no crystal structure of a W(0) hexakis(alkylisocyanide) complex exists, while for W(II) only [W(CNtBu)7] 2+ has been structurally characterized. Therefore, we decided to use DFT calculations (M06L/Def2-TZVP)