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(CH₂SiMe₃)] (TriNOx^3- = [(2-^tBuNO)C₆H₄CH₂]₃N)^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 Heteroatom-Transfer Ligand (HTL) platform.