A zwitterionic phosphonium stannate(II) via hydrogen splitting by a Sn/P frustrated Lewis‐pair and reductive elimination
Holtkamp, Philipp; Schwabedissen, Jan; Neumann, Beate; Stammler, Hans-Georg; Koptyug, Igor V.; Zhivonitko, Vladimir V.; Mitzel, Norbert W. (2020-10-05)
P. Holtkamp, J. Schwabedissen, B. Neumann, H.-G. Stammler, I. V. Koptyug, V. V. Zhivonitko, N. W. Mitzel, Chem. Eur. J. 2020, 26, 17381. https://doi.org/10.1002/chem.202004425
© 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
https://creativecommons.org/licenses/by-nc-nd/4.0/
https://urn.fi/URN:NBN:fi-fe202101121623
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Abstract
The reactivity of the frustrated Lewis pair (FLP) (F₅C₂)₃SnCH₂P(tBu)₂ (1) was investigated with respect to the activation of elemental hydrogen. The reaction of 1 at elevated hydrogen pressure afforded the intramolecular phosphonium stannate(II) (F₅C₂)₂SnCH₂PH(tBu)₂ (3). It was characterized by means of multinuclear NMR spectroscopy and single crystal X‐ray diffraction. NMR experiments with the two isotopologues H₂ and D₂ showed it to be formed via an H₂ adduct (F₅C₂)₃HSnCH₂PH(tBu)₂ (2) and the subsequent formal reductive elimination of pentafluoroethane; this is supported by DFT calculations. Parahydrogen‐induced polarization experiments revealed the formation of a second product of the reaction of 1 with H₂, [HP(tBu)₂Me][Sn(C₂F₅)₃] (4), in ¹H NMR spectra, whereas 2 was not detected due to its transient nature.
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