Chemistry - A European Journal p. 2025 - 2034 (2019)
Update date:2022-08-25
Topics:
Pahl, Jürgen
Stennett, Tom E.
Volland, Michel
Guldi, Dirk M.
Harder, Sjoerd
[(BDI)Mg+][B(C6F5)4?] (1; BDI=CH[C(CH3)NDipp]2; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4?]. Addition of 3-hexyne gave [(BDI)Mg+?(EtC≡CEt)][B(C6F5)4?]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg+(C≡CPh)]2?2 [B(C6F5)4?] (2, 70 %) and [(BDI-H)Mg+(C≡CSiMe3)]2?2 [B(C6F5)4?] (3, 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2? 2 [B(C6F5)4?] (4, 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2?2 [B(C6F5)4?] (5, 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Br?nsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4?] (1) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+?PPh3][B(C6F5)4?] (6), [(BDI)Mg+?PCy3][B(C6F5)4?] (7), and [(BDI)Mg+? PtBu3][B(C6F5)4?] (8). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4?] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP-type mechanism is tentatively proposed.
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