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Abstract
A theoretical mechanistic study for a Heck-Matsuda reaction mediated by nickel complexes was performed using DFT calculations considering 3-cyclopenten-1-ol as the initial olefin. Two pathways were identified: a closed shell singlet Ni(0)/Ni(II) and an open shell doublet Ni(I)/Ni(III). Analysis of kinetic energy profiles through span analysis revealed a pivotal shift in rate-determining states. This shift is influenced by the rotational flexibility of the starting olefin during $\beta$-hydride elimination and the base strength during reductive elimination. Notably, both pathways yielded identical stereochemistry, governed by the interaction of the hydroxyl group with the metal center. The mechanistic hypothesis was later tested in a case study using styrene as olefin yielding a TOF closely aligned with analogue experimental data. The pre-catalysis thermodynamic profile favoured the doublet catalytic cycle over the singlet counterpart in the presence of aryl radical species. These theoretical insights offer practical guidance for enhancing synthetic methodologies.
Supplementary materials
Title
S.I.-The rate-determining states of Nickel based Heck-Matsuda Reaction can be modulated: Theoretical insights and their synthetic implications
Description
A theoretical mechanistic study for a Heck-Matsuda reaction mediated by nickel complexes was performed using DFT calculations considering 3-cyclopenten-1-ol as the initial olefin. Two pathways were identified: a closed shell singlet Ni(0)/Ni(II) and an open shell doublet Ni(I)/Ni(III). Analysis of kinetic energy profiles through span analysis revealed a pivotal shift in rate-determining states. This shift is influenced by the rotational flexibility of the starting olefin during $\beta$-hydride elimination and the base strength during reductive elimination. Notably, both pathways yielded identical stereochemistry, governed by the interaction of the hydroxyl group with the metal center. The mechanistic hypothesis was later tested in a case study using styrene as olefin yielding a TOF closely aligned with analogue experimental data. The pre-catalysis thermodynamic profile favoured the doublet catalytic cycle over the singlet counterpart in the presence of aryl radical species. These theoretical insights offer practical guidance for enhancing synthetic methodologies.
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