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A Zwitterionic Phosphonium Stannate(II) via Hydrogen Splitting by a Sn/P Frustrated Lewis-Pair and Reductive Elimination.

Authors :
Holtkamp P
Schwabedissen J
Neumann B
Stammler HG
Koptyug IV
Zhivonitko VV
Mitzel NW
Source :
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2020 Dec 23; Vol. 26 (72), pp. 17381-17385. Date of Electronic Publication: 2020 Nov 23.
Publication Year :
2020

Abstract

The reactivity of the frustrated Lewis pair (FLP) (F <subscript>5</subscript> C <subscript>2</subscript> ) <subscript>3</subscript> SnCH <subscript>2</subscript> P(tBu) <subscript>2</subscript> (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) (F <subscript>5</subscript> C <subscript>2</subscript> ) <subscript>2</subscript> SnCH <subscript>2</subscript> PH(tBu) <subscript>2</subscript> (3). It was characterized by means of multinuclear NMR spectroscopy and single crystal X-ray diffraction. NMR experiments with the two isotopologues H <subscript>2</subscript> and D <subscript>2</subscript> showed it to be formed via an H <subscript>2</subscript> adduct (F <subscript>5</subscript> C <subscript>2</subscript> ) <subscript>3</subscript> HSnCH <subscript>2</subscript> PH(tBu) <subscript>2</subscript> (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 H <subscript>2</subscript> , [HP(tBu) <subscript>2</subscript> Me][Sn(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> ] (4), in <superscript>1</superscript> H NMR spectra, whereas 2 was not detected due to its transient nature.<br /> (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3765
Volume :
26
Issue :
72
Database :
MEDLINE
Journal :
Chemistry (Weinheim an der Bergstrasse, Germany)
Publication Type :
Academic Journal
Accession number :
33016507
Full Text :
https://doi.org/10.1002/chem.202004425