Pyrrole-Based Ti(III) and Ti(IV) PNP Pincer Complexes: Insertion of Ketones into the Ti(IV)-Phosphorus Bond

[Image: see text] The synthesis, characterization, and reactivity of pyrrole-based Ti(III) and Ti(IV) PNP pincer complexes are described. [P(NH)P-iPr] (1) reacts with [TiCl(4)(THF)(2)] at room temperature in the presence of NEt(3) to afford the Ti(IV) complex [Ti(PNP(iPr))(Cl)(3)]. This complex reacts with acetone and cyclopentanone to give complexes [Ti(PNO(acet)-iPr)(Cl)(3)] and [Ti(PNO(cyclo)-iPr)(Cl)(3)], respectively. Insertion of the ketone into the Ti(IV)-P bond took place, forming a new tridendate PNO-ligand. Treatment of [TiCl(3)(THF)(3)] with the lithium salt of [P(NH)P-iPr] afforded, upon workup, complex [Ti(PNP-iPr)(Cl)(2)(THF)], a paramagnetic complex with an μ(eff) value of 1.8(1) μ(B) which corresponds to one unpaired electron and a formal oxidation state of +III. This compound does not react with ketones. A mechanistic proposal based on DFT calculations is presented. Ketone insertion proceeds via an associative reaction initiated by ketone coordination at the metal center, followed by the opening of the five-membered chelate ring, and finally an intramolecular nucleophilic attack of the noncoordinated phosphine arm at the carbonyl atom of the ketone. All complexes were characterized by X-ray crystallography.