N₂ Functionalization at Iron Metallaboratranes

The reactivity of the anionic dinitrogen complex [(TPB)Fe(N(2))](-) (TPB = tris[2-(diisopropylphosphino)phenyl]borane) toward silicon electrophiles has been examined. [(TPB)Fe(N(2))](-) reacts with trimethylsilyl chloride to yield the silyldiazenido complex (TPB)Fe(NNSiMe(3)), which is reduced by Na/Hg in THF to yield the corresponding sodium-bound anion [(TPB)Fe(NNSiMe(3))]Na(THF). The use of 1,2-bis(chlorodimethylsilyl)ethane in the presence of excess Na/Hg results in the disilylation of the bound N(2) molecule to yield the disilylhydrazido(2-) complex (TPB)Fe≡NR (R = 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl). One of the phosphine arms of TPB in (TPB)Fe≡NR can be substituted by CO or (t)BuNC to yield crystalline adducts (TPB)(L)Fe≡NR (L = CO, (t)BuNC). The N-N bond in (TPB)((t)BuNC)Fe≡NR is cleaved upon standing at room temperature to yield a phosphoraniminato/disilylamido iron(II) complex. The flexibility of the Fe-B linkage is thought to play a key role in these transformations of Fe-bound dinitrogen.