A Tautomeric [lamda]3/[lambda]5-phosphane pair and its ambiphilic reactivity
The central phosphorus atom of a novel hydroxyl-functionalized triarylphosphane was shown to reversibly insert into one of the molecule’s O-H bonds, which forms the basis for a tautomeric λ3/λ5-phosphane equilibrium. For the first time, this equilibrium was detected for a λ3-triarylphosphane and the...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
February 19, 2019
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| In: |
Inorganic chemistry
Year: 2019, Volume: 58, Issue: 5, Pages: 3502-3508 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.9b00076 |
| Online Access: | Verlag, Volltext: https://doi.org/10.1021/acs.inorgchem.9b00076
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| Author Notes: | Jean-Marc Mörsdorf, Hubert Wadepohl, and Joachim Ballmann |
| Summary: | The central phosphorus atom of a novel hydroxyl-functionalized triarylphosphane was shown to reversibly insert into one of the molecule’s O-H bonds, which forms the basis for a tautomeric λ3/λ5-phosphane equilibrium. For the first time, this equilibrium was detected for a λ3-triarylphosphane and the underlying dynamic process was elucidated by NMR spectroscopy. On the basis of reactivity studies, a nucleophilic character was assigned to the minor species present in solution, the λ3-phosphane. Upon methylation, for example, the λ3-form was selectively removed from the equilibrium and converted to the corresponding phosphonium salt. However, upon generation of an alkoxide via proton abstraction, the electrophilic character of the λ5-phosphane in the equilibrium became evident since the alkoxide was found to attack the molecule’s phosphorus atom. This intramolecular reaction led to the selective formation of a new anionic λ6-hydridospirophosphane. |
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| Item Description: | Gesehen am 02.05.2019 |
| Physical Description: | Online Resource |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.9b00076 |