Ethereal C-O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

Area of Science:

• Organometallic Chemistry
• Catalysis
• Computational Chemistry

Background:

• Nickel-catalyzed cross-coupling reactions are vital in organic synthesis.
• Ethereal C-O bond cleavage presents a challenge in these reactions.
• Previous studies investigated the Kumada-Tamao reaction mechanism.

Purpose of the Study:

• To elucidate the mechanism of Ni-catalyzed cross-coupling reactions involving organo-lithium and organo-zinc reagents.
• To investigate the role of ethereal C-O bond cleavage in these reactions.
• To identify and characterize a novel catalytic cycle.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• Mechanistic analysis of Ni-catalyzed reactions was performed.
• Comparison with previous studies on the Kumada-Tamao reaction.

Main Results:

• The mechanism of Ni-catalyzed cross-coupling via ethereal C-O bond cleavage was explored.
• A novel catalytic cycle mediated by a Ni(0)-ate complex was identified.
• The catalytic cycle provides new insights into ether functionalization.

Conclusions:

• The study successfully characterized a novel catalytic cycle for Ni-mediated cross-coupling.
• This work advances the understanding of reactions involving ethereal C-O bond cleavage.
• The findings contribute to the development of new synthetic methodologies.