Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation.

Transition metal carbyne complexes are of fundamental importance in carbon-carbon bond formation, alkyne metathesis, and alkyne coupling reactions. Most reported iron carbyne complexes are stabilized by incorporating heteroatoms. Here we show the synthesis of bioinspired FeMo heterobimetallic carbyne complexes by the conversion of CH through a diverse series of intermediates. Key reactions discovered include the reduction of a μ-η:η-CH ligand with a hydride to produce a vinyl ligand (μ-η:η-CH = CH), tautomerization of the vinyl ligand to a carbyne (μ-CCH), and protonation of either the vinyl or the carbyne compound to form a hydrido carbyne heterobimetallic complex. Mechanistic studies unveil the pivotal role of HO as a proton shuttle, facilitating the proton transfer that converts the vinyl group to a bridging carbyne.