Cerium(III) yldiide complexes with divergent CO reactivity.

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Computational Chemistry

Background:

• Cerium ylide complexes represent an emerging class of organometallic compounds.
• Understanding their reactivity is crucial for developing new synthetic methodologies.
• The interaction of metal complexes with small molecules like carbon monoxide is a fundamental area of study.

Purpose of the Study:

• To demonstrate the synthesis of novel cerium ylide complexes.
• To investigate the reactivity of these complexes with carbon monoxide (CO).
• To elucidate the mechanistic pathways governing the observed product distributions.

Main Methods:

• Synthesis of sulfur-tethered and tosyl-substituted cerium ylide complexes.
• Reaction of synthesized complexes with carbon monoxide.
• Product characterization and computational analysis (e.g., DFT) to study reaction mechanisms.

Main Results:

• The sulfur-tethered ylide yielded a ketenyl complex with triphenylphosphine (PPh3) release.
• The tosyl-substituted ylide produced Ph3PCCO and a sulfinato ligand.
• Computational studies indicated that the differing stability of isomeric intermediates dictates the reaction pathway.

Conclusions:

• The reactivity of cerium ylide complexes with CO is highly dependent on the nature of the ylide substituent.
• Distinct mechanistic pathways are operative for sulfur-tethered versus tosyl-substituted ylides.
• Intermediate stability plays a critical role in determining the final product outcome in these reactions.