C_S-Symmetric Pyridine(diimine) Iron Methyl Complexes for Catalytic [2+2] Cycloaddition and Hydrovinylation: Metallacycle Geometry Determines Selectivity.

ABSTRACT: A series of C_S-symmetric (aryl,alkyl)-substituted pyridine(dimine) iron methyl (^CyA^RPDI)FeCH₃ complexes have been prepared, characterized, and evaluated as precatalysts for the [2+2]-cycloaddition of butadiene and ethylene. Mixtures of vinylcyclobutane and (Z)-hexa-1,4-diene were observed in each case. By comparison, C_2v-symmetric, arylated (PDI) iron catalysts are exclusively selective for reversible [2+2]-cycloaddition to yield vinylcyclobutane. The alteration in the chemoselectivity of the catalytic reaction was investigated through a combination of precatalyst stability studies, identification of catalytic resting state(s), and ²H and ¹³C isotopic labeling experiments. While replacement of

SUBMITTER: Duchemin C 

PROVIDER: S-EPMC10369671 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature