Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu(2)P–P(SiMe(3)) Ligand

[Image: see text] We present two important trends in the reactivity of the titanium complex [(Me)NacNacTi(Cl){η(2)-P(SiMe(3))-PtBu(2)}] ((Me)NacNac(–) = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr(2)Ph) with nucleophilic reagents RLi (R = Ph(2)P, tBuO, (Me(3)Si)(2)N, and tBu(2)N) depending on the reaction medium. Reaction in nonpolar solvent (toluene) leads to three main products: via an autoredox process and nucleophilic substitution at the Ti-atom to afford the Ti(IV) complex [(Me)NacNacTi(R){η(2)-P-PtBu(2)}] (1 for R = PPh(2)), via the elimination of Me(3)SiR to afford Ti(III) complex [(Me)NacNacTi(Cl){η(2)-P-PtBu(2)}](−)[Li(12-crown-4)(2)](+) (2), and via 2e(–) reduction process to afford new ionic complex [{ArNC(Me)CHC(Me)}Ti=NAr{η(1)-P(SiMe(3))-PtBu(2)}](−)[Li(12-crown-4)(2)](+) (3). Quite differently, the complex [(Me)NacNacTi(Cl){η(2)-P(SiMe(3))-PtBu(2)}] reacts with Ph(2)PLi in THF, unexpectedly yielding two new, four-coordinate Ti(IV) imido complexes 4a [{ArNC(Me)=CHC(H)(Me)-P(PtBu(2))}Ti=NAr(Cl)](−)[Li(12-crown-4)(2)](+)·(toluene)(2) and 4b [{ArNC(CH(2))CH=C(Me)-P(PtBu(2))}Ti=NAr(Cl)](−)[Li(12-crown-4)(2)](+)·(Et(2)O). Complex 2 dissolved in THF converts to 4a and 4b. 1, 2, 3, 4a, and 4b were characterized by X-ray diffraction. 1, 4a, and 4b were also fully characterized by multinuclear NMR spectroscopy.