Publications Repository - Gdańsk University of Technology

We present two important trends in the reactivity ofthe 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, andtBu2N) depending on the reaction medium. Reaction in nonpolarsolvent (toluene) leads to three main products: via an autoredoxprocess and nucleophilic substitution at the Ti-atom to afford theTi(IV) complex [MeNacNacTi(R){η2-P-PtBu2}] (1for R = PPh2),via the elimination of Me3SiR to afford Ti(III) complex[MeNacNacTi(Cl){η2-P-PtBu2}]−[Li(12-crown-4)2]+(2), and via2e−reduction process to afford new ionic complex [{ArNC(Me)-CHC(Me)}TiNAr{η1-P(SiMe3)-PtBu2}]−[Li(12-crown-4)2]+(3). Quite differently, the complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}] reacts with Ph2PLi in THF, unexpectedly yielding two new, four-coordinate Ti(IV) imido complexes4a[{ArNC(Me)CHC(H)(Me)-P(PtBu2)}TiNAr(Cl)]−[Li(12-crown-4)2]+·(toluene)2and4b[{ArNC(CH2)CHC(Me)-P(PtBu2)}TiNAr-(Cl)]−[Li(12-crown-4)2]+·(Et2O). Complex2dissolved in THF converts to4aand4b.1,2,3,4a, and4bwere characterized by X-ray diffraction.1,4a, and4bwere also fully characterized by multinuclear NMR spectroscopy.

Authors

• dr inż. Aleksandra Ziółkowska link open in new tab ,
• mgr inż. Natalia Szynkiewicz link open in new tab ,
• prof. dr hab. inż. Jerzy Pikies link open in new tab ,
• dr hab. inż. Łukasz Ponikiewski link open in new tab