Realization of a Heteroatom‐Transfer‐Ligand (HTL) Platform: Oxy Insertion at a Titanium–Alkyl Bond Facilitated by a Hydroxylaminato Ligand Framework

Abstract Selective oxidation of metal‐carbon bonds is arguably one of the most important reactions in modern chemistry. In this work, we report the synthesis and the reactivity of a titanium alkyl complex [(TriNOx)Ti(CH 2 SiMe 3 )] (TriNOx 3− = [(2‐ t BuNO)C 6 H 4 CH 2 ] 3 N) 3– ) that was found to undergo an internal rearrangement through an oxy‐insertion into the Ti─C bond facilitated by one of the hydroxylaminato moieties of the supporting TriNOx 3− ligand. Experimental and computational studies are in agreement with an organometallic Baeyer–Villiger‐type mechanism. Furthermore, stepwise dealkoxylation, reoxidation, and alkylation of the resulting complex allowed for closing a synthetic cycle and regenerating the initial starting complex. This work demonstrates the unique ability of the TriNOx 3− ligand to mediate and manage O‐atoms in the coordination sphere of a titanium cation and delineates a new type of metal‐ligand cooperativity through a H eteroatom‐ T ransfer L igand (HTL) platform.