Oxidative Addition of a Phosphinite P-O Bond at Nickel.

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-OP i Pr 2 -3,5- t Bu-C 6 H 2 ) 2 [H(P 2 ONO)] at Ni 0 to form (PONO)Ni(HP i Pr 2 ) 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 XPR 2 (X = Cl, Br; R = i Pr, Cy) to (PONO)Ni(HP i Pr 2 ) readily produces either symmetric or unsymmetric (P 2 ONO)NiX species and free HP i Pr 2 . 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.