<i>Z</i>‑Selective Alkene Isomerization by High-Spin Cobalt(II) Complexes

The isomerization of simple terminal alkenes to internal isomers with Z-stereochemistry is rare, because the more stable E-isomers are typically formed. We show here that cobalt­(II) catalysts supported by bulky β-diketiminate ligands have the appropriate kinetic selectivity to catalyze the isomerization of some simple 1-alkenes specifically to the 2-alkene as the less stable Z-isomer. The catalysis proceeds via an “alkyl” mechanism, with a three-coordinate cobalt­(II) alkyl complex as the resting state. β-Hydride elimination and [1,2]-insertion steps are both rapid, as shown by isotopic labeling experiments. A steric model explains the selectivity through a square-planar geometry at cobalt­(II) in the transition state for β-hydride elimination. The catalyst works not only with simple alkenes, but also with homoallyl silanes, ketals, and silyl ethers. Isolation of cobalt­(I) or cobalt­(II) products from reactions with poor substrates suggests that the key catalyst decomposition pathways are bimolecular, and lowering the catalyst concentration often improves the selectivity. In addition to a potentially useful, selective transformation, these studies provide a mechanistic understanding for catalytic alkene isomerization by high-spin cobalt complexes, and demonstrate the effectiveness of steric bulk in controlling the stereoselectivity of alkene formation.