Water-Driven Isomerization Control: Dinuclear Cobalt-Catalyzed Monoisomerization of Linear Terminal Alkenes

The development of binuclear earth-abundant metal catalytic systems, drawing inspiration from metalloenzymes, has attracted considerable research interest in homogeneous catalysis. While current catalytic systems for alkene isomerization are mainly limited to monometallic catalysis, emerging opportunities in dinuclear catalysis present transformative potential, although their working mechanisms are still elusive. Herein, a dinuclear cobalt complex-catalyzed monoisomerization of linear alkyl α-olefins to 2-alkenes is disclosed, which is unusual because H₂O is found to play a significant role in the control of regioselectivity, turning a mixture of multiisomers into 2-alkenes in high yields with excellent regioselectivity. DFT calculations indicated that the hydroxyl exchange step between H₂O and the Co–H active intermediate acts as a functional hindrance to control the site selectivity for the selective monoisomerization.