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The activity of nitrogenase enzymes, which catalyze the conversion of atmospheric dinitrogen to bioavailable ammonia, is most commonly assayed by the reduction of acetylene gas to ethylene. Despite the practical importance of acetylene as a substrate, little is known concerning its binding or activation in the iron-rich active site. "Fischer-Tropsch" type coupling of non-native C 1 substrates to higher-order C ≥2 products is also known for nitrogenase, though potential metal-carbon multiply bonded intermediates remain underexplored. Here we report the activation of acetylene gas at a mononuclear tris(phosphino)silyl-iron center, (SiP 3 )Fe, to give Fe(I) and Fe(II) side-on adducts, including S = 1/2 Fe I (η 2 -HCCH); the latter is characterized by pulse EPR spectroscopy and DFT calculations. Reductive protonation reactions with these compounds converge at stable examples of unusual, formally iron(IV) and iron(V) carbyne complexes, as in diamagnetic (SiP 3 )Fe≡CCH 3 and the paramagnetic cation S = 1/2 [(SiP 3 )Fe≡CCH 3 ] + . Both alkylcarbyne compounds possess short Fe-C triple bonds (approximately 1.7 Å) trans to the anchoring silane. Pulse EPR experiments, X-band ENDOR and HYSCORE, reveal delocalization of the iron-based spin onto the α-carbyne nucleus in carbon p-orbitals. Furthermore, isotropic coupling of the distal β-CH 3 protons with iron indicates hyperconjugation with the spin/hole character on the Fe≡CCH 3 unit. The electronic structures of (SiP 3 )Fe≡CCH 3 and [(SiP 3 )Fe≡CCH 3 ] + are discussed in comparison to previously characterized, but heterosubstituted, iron carbynes, as well as a hypothetical nitride species, (SiP 3 )Fe≡N. Such comparisons are germane to the consideration of formally high-valent, multiply bonded Fe≡C and/or Fe≡N intermediates in synthetic or biological catalysis by iron.

Mononuclear Fe(I) and Fe(II) Acetylene Adducts and Their Reductive Protonation to Terminal Fe(IV) and Fe(V) Carbynes