The Spin States of the Preactivation of Cationic Cobalt(II) Catalysts in Hydroformylation: A DFT Mechanistic Understanding

Abstract The spin states of cobalt-based catalysts play a crucial role in the catalytic performance. In this study, the spin states of the activation of [Co(acac)(DEPBz)](BF4) catalyst precursors were investigated using the density functional theory (DFT) method. The calculated results show that high-spin (quartet) species observed by electron paramagnetic resonance (EPR) spectroscopy in experiments could not be the catalytically active species in the reaction but rather solvent-coordinated species or Co(acac)2DEPBz. This could provide interesting theoretical insights into hydroformylation tuned by the spin-state behavior of cobalt-based catalysts and provide theoretical guidance for the design of efficient 3d metal catalysts.