A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair

Krieft J, Trapp P, Vishnevskiy Y, Neumann B, Stammler H-G, Lamm J-H, Mitzel NW (2024)
Chemical Science.

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Abstract / Bemerkung
The geminal Lewis pair (F5C2)(2)SbCH2P(tBu)(2) (1) was prepared by reacting (F5C2)(2)SbCl with LiCH2P(tBu)(2). Despite its extremely electronegative pentafluoroethyl substituents, the neutral 1 exhibits a relatively soft acidic antimony function according to the HSAB concept (hard-soft acid-base). These properties lead to a reversibility in the binding of CS2 to 1, as observed by VT-NMR spectroscopy, while no reaction with CO2 is observed. The reaction behaviour towards heterocumulenes and the specific interaction situation in the CS2 adduct were analysed by quantum chemical calculations. The FLP-type reactivity of 1 has also been demonstrated by reaction with a variety of small molecules (SO2, PhNCO, PhNCS, (MePh2P)AuCl). The reactions of 1 with PhNCO and PhNCS led to different types of cyclic addition products: PhNCO adds with its N-C bond and PhNCS adds preferentially with its CS bond. The reaction of 1 with (MePh2P)AuCl gave an adduct {[(F5C2)(2)SbCH2(tBu)(2)P](2)Au}(+) with a clamp-like structure binding a chloride anion by its two antimony atoms in chelate mode. Compound 1 and its adducts have been characterised by X-ray diffraction experiments, multinuclear NMR spectroscopy, elemental analyses and computational calculations (DFT, QTAIM, IQA).
Erscheinungsjahr
2024
Zeitschriftentitel
Chemical Science
ISSN
2041-6520
eISSN
2041-6539
Page URI
https://pub.uni-bielefeld.de/record/2991448

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Krieft J, Trapp P, Vishnevskiy Y, et al. A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair. Chemical Science. 2024.
Krieft, J., Trapp, P., Vishnevskiy, Y., Neumann, B., Stammler, H. - G., Lamm, J. - H., & Mitzel, N. W. (2024). A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair. Chemical Science. https://doi.org/10.1039/d4sc02785j
Krieft, Jonas, Trapp, Pia, Vishnevskiy, Yury, Neumann, Beate, Stammler, Hans-Georg, Lamm, Jan-Hendrik, and Mitzel, Norbert W. 2024. “A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair”. Chemical Science.
Krieft, J., Trapp, P., Vishnevskiy, Y., Neumann, B., Stammler, H. - G., Lamm, J. - H., and Mitzel, N. W. (2024). A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair. Chemical Science.
Krieft, J., et al., 2024. A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair. Chemical Science.
J. Krieft, et al., “A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair”, Chemical Science, 2024.
Krieft, J., Trapp, P., Vishnevskiy, Y., Neumann, B., Stammler, H.-G., Lamm, J.-H., Mitzel, N.W.: A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair. Chemical Science. (2024).
Krieft, Jonas, Trapp, Pia, Vishnevskiy, Yury, Neumann, Beate, Stammler, Hans-Georg, Lamm, Jan-Hendrik, and Mitzel, Norbert W. “A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair”. Chemical Science (2024).

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