Cerium(III) yldiide complexes with divergent CO reactivity

Abstract

Synthesis of cerium yldiide complexes and their reactivity with CO is demonstrated. In the case of the sulphur-tethered yldiide, the ketenyl complex is formed with release of PPh₃, while Ph₃PCCO is formed along with a sulfinato ligand in the case of the tosyl-substituted yldiide. Computational analysis shows that this diverging reactivity is due to the stability of the two isomers in the first step of each mechanism.