Selective Oxidation of Tertiary Silanes Enabled by Tandem Single Atom Cerium Catalyzed Water Splitting/Non‐Bonding Phosphorus Site Promoted Nucleophilic Substitution

Abstract

ABSTRACT The utilization of heterogeneous catalysts, particularly single‐atom catalysts (SACs), to mimic or even supplant their homogeneous counterparts for building complex molecular architectures is a long‐standing objective in sustainable chemistry, however it remains a formidable challenge to date. Herein, we report a selective oxidation of tertiary silanes through a tandem process combining single‐atom cerium‐catalyzed water splitting with nucleophilic substitution promoted by a non‐bonding phosphorus site. This approach yields either silanols or siloxanes with exclusive selectivity and promising reusability. In the Ce‐SA/CN catalyst, the redox shuttle of the atomically dispersed cerium center activates water to hydroxylate SiH bond while suppressing silanol condensation. In contrast, the introduction of phosphorus sites in Ce‐SA/CNP creates an adjacent Lewis basic site that recruits and activates the –OH group of nascent silanols, thereby driving efficient interfacial dehydration to form disiloxanes. This work underscores microenvironment engineering of SACs as a pivotal strategy for steering complex reaction pathways and establishes a versatile platform for precise synthesis.