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

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.