om6b00474_si_002.cif (117.87 kB)

Mechanistic Insight Into High-Spin Iron(I)-Catalyzed Butadiene Dimerization

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posted on 19.08.2016, 15:34 by Heejun Lee, Michael G. Campbell, Raúl Hernández Sánchez, Jonas Börgel, Jean Raynaud, Sarah E. Parker, Tobias Ritter
Iron complexes are commonly used in catalysis, but the identity of the active catalyst is often unknown, which prevents a detailed understanding of structure–reactivity relationships for catalyst design. Here we report the isolation and electronic structure determination of a well-defined, low-valent iron complex that is an active catalyst in the synthesis of cis,cis-1,5-cyclooctadiene (COD) from 1,3-butadiene. Spectroscopic and magnetic characterization establishes a high-spin Fe­(I) center, which is supported by DFT studies, where partial metal–ligand antibonding orbital population is proposed to allow for facile ligand exchange during catalysis.