A highly reactive geminal P/B frustrated Lewis pair: expanding the scope to C−X (X=Cl, Br) bond activation
- The geminal frustrated Lewis pair tBu2PCH2B(Fxyl)2 (1; Fxyl=3,5-(CF3)2C6H3) is accessible in 65 % yield from tBu2PCH2Li and (Fxyl)2BF. According to NMR spectroscopy and X-ray crystallography, 1 is monomeric both in solution and in the solid state. The intramolecular P⋅⋅⋅B distance of 2.900(5) Å and the full planarity of the borane site exclude any significant P/B interaction. Compound 1 readily activates a broad variety of substrates including H2, EtMe2SiH, CO2/CS2, Ph2CO, and H3CCN. Terminal alkynes react with heterolysis of the C−H bond. Haloboranes give cyclic adducts with strong P−BX3 and weak R3B−X bonds. Unprecedented transformations leading to zwitterionic XP/BCX3 adducts occur on treatment of 1 with CCl4 or CBr4 in Et2O. In less polar solvents (C6H6, n-pentane), XP/BCX3 adduct formation is accompanied by the generation of significant amounts of XP/BX adducts. FLP 1 catalyzes the hydrogenation of PhCH=NtBu and the hydrosilylation of Ph2CO with EtMe2SiH.
Author: | Kamil Samigullin, Isabelle Georg, Michael BolteORCiD, Hans-Wolfram LernerORCiDGND, Matthias WagnerORCiD |
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URN: | urn:nbn:de:hebis:30:3-422469 |
DOI: | https://doi.org/10.1002/chem.201504791 |
ISSN: | 0947-6539 |
Parent Title (English): | Chemistry |
Publisher: | Wiley-VCH |
Place of publication: | Weinheim |
Document Type: | Article |
Language: | English |
Date of Publication (online): | 2016/11/26 |
Date of first Publication: | 2016/02/02 |
Publishing Institution: | Universitätsbibliothek Johann Christian Senckenberg |
Release Date: | 2016/12/21 |
Volume: | 22 |
Issue: | 10 |
Page Number: | 7 |
First Page: | 3478 |
Last Page: | 3484 |
Note: | http://creativecommons.org/licenses/by-nc-nd/4.0/ |
HeBIS-PPN: | 427892376 |
Institutes: | Biochemie, Chemie und Pharmazie / Biochemie und Chemie |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Sammlungen: | Universitätspublikationen |
Licence (German): | Creative Commons - Namensnennung-Nicht kommerziell - Keine Bearbeitung 4.0 |