Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand - Publication - Bridge of Knowledge

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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand

Abstract

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.

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Category:
Articles
Type:
artykuły w czasopismach
Published in:
INORGANIC CHEMISTRY no. 59, pages 11305 - 11315,
ISSN: 0020-1669
Language:
English
Publication year:
2020
Bibliographic description:
Ziółkowska A., Szynkiewicz N., Pikies J., Ponikiewski Ł.: Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand// INORGANIC CHEMISTRY -Vol. 59,iss. 16 (2020), s.11305-11315
DOI:
Digital Object Identifier (open in new tab) 10.1021/acs.inorgchem.0c00824
Verified by:
Gdańsk University of Technology

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