University of Oulu

P. Holtkamp, J. Schwabedissen, B. Neumann, H.-G. Stammler, I. V. Koptyug, V. V. Zhivonitko, N. W. Mitzel, Chem. Eur. J. 2020, 26, 17381.

A zwitterionic phosphonium stannate(II) via hydrogen splitting by a Sn/P frustrated Lewis‐pair and reductive elimination

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Author: Holtkamp, Philipp1; Schwabedissen, Jan1; Neumann, Beate1;
Organizations: 1Lehrstuhl für Anorganische Chemie und Strukturchemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, 33615 Bielefeld, Germany
2International Tomography Center, SB RAS, Institutskaya St. 3A, Novosibirsk, 630090 Russia
3NMR Research Unit, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 0.8 MB)
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Language: English
Published: John Wiley & Sons, 2020
Publish Date: 2021-01-12


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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Series: Chemistry. A European journal
ISSN: 0947-6539
ISSN-E: 1521-3765
ISSN-L: 0947-6539
Volume: 26
Issue: 72
Pages: 17381 - 17385
DOI: 10.1002/chem.202004425
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: We gratefully acknowledge financial support from Deutsche Forschungsgemeinschaft (DFG, grant MI477/31‐1 project no. 320753677, N.W.M.), the Academy of Finland (grant no. 323480, V.V.Z.), the RFBR (#19‐29‐10003, I.V.K.) and computing time provided by the Paderborn Center for Parallel Computing (PC2). Open access funding enabled and organized by Projekt DEAL.
Academy of Finland Grant Number: 323480
Detailed Information: 323480 (Academy of Finland Funding decision)
Dataset Reference: Deposition Number 2025485 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service
Copyright information: © 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.