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

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.