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We present two important trends in the reactivity of the titanium complex [MeNacNacTi(Cl)η2-P(SiMe3)-PtBu2] (MeNacNac- = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2Ph) with nucleophilic reagents RLi (R = Ph2P, tBuO, (Me3Si)2N, and tBu2N) 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 [MeNacNacTi(R)η2-P-PtBu2] (1 for R = PPh2), via the elimination of Me3SiR to afford Ti(III) complex [MeNacNacT
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