LAUSR

Oxidative addition is an essential elementary reaction in organometallic chemistry and catalysis. While a diverse array of oxidative addition reactions has been reported to date, examples of P-O bond activation are surprisingly rare. Herein, we report the ligand-templated oxidative addition of a phosphinite P-O bond in the diphosphinito aniline compound HN(2-OPiPr2-3,5-tBu-C6H2)2 [H(P2ONO)] at Ni0 to form (PONO)Ni(HPiPr2) after proton rearrangement. Notably, the P-O cleavage occurs selectively over an amine N-H bond activation. Additionally, the ligand cannibalization is reversible, as addition of XPR2 (X = Cl, Br; R = iPr, Cy) to (PONO)Ni(HPiPr2) readily produces either symmetric or unsymmetric (P2ONO)NiX species and free HPiPr2. Finally, the mechanisms of both the initial P-O bond cleavage and its subsequent reconstruction are investigated to provide further insight into how to target P-O bond activation.