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Monomeric Triphosphinoboranes: Intramolecular Lewis Acid–Base Interactions between Boron and Phosphorus Atoms
Abstrakt
Herein, we present the synthesis of the first fully characterized monomeric triphosphinoboranes. The simple reaction of boron tribromide with three equivalents of bulky lithium phosphide tBu2PLi yielded triphosphinoborane (tBu2P)3B. Triphosphinoboranes with diversified phosphanyl substituents were obtained via a two-step reaction, in which isolable bromodiphosphinoborane (tBu2P)2BBr is first formed and then reacts with one equivalent of less bulky phosphide R2PLi (R2P = Cy2P, iPr2P, tBuPhP, Ph2P). By utilizing this method, we obtained a series of triphosphinoboranes with the general formula (tBu2P)2BPR2. Based on structural and theoretical studies, two main types of triphosphinoborane structures can be distinguished. In the first type, all three electron lone pairs interact with the formally empty p-orbital of the central boron atom, resulting in delocalized π-bonding, whereas in the second type, one localized double P=B bond and two single P-B bonds are observed. The Lewis acidic-basic properties of triphosphinoboranes during the reaction of (tBu2P)2BPiPr2 with H3B·SMe2 were analyzed. The abovementioned P-B bond-containing compound not only formed an adduct with BH3 but also activated the B-H bond of the borane molecule, resulting in the incorporation of the BH2 unit into two phosphorus atoms and migration of a hydride to the boron atom of the parent triphosphinoborane. The structures of the triphosphinoboranes were confirmed by single crystal X-ray analysis, multinuclear NMR spectroscopy, and elemental analysis.
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- Wersja publikacji
- Accepted albo Published Version
- DOI:
- Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1021/acs.inorgchem.1c03618
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Informacje szczegółowe
- Kategoria:
- Publikacja w czasopiśmie
- Typ:
- artykuły w czasopismach
- Opublikowano w:
-
INORGANIC CHEMISTRY
nr 61,
strony 4361 - 4370,
ISSN: 0020-1669 - Język:
- angielski
- Rok wydania:
- 2022
- Opis bibliograficzny:
- Ordyszewska A., Szynkiewicz N., Chojnacki J., Grubba R.: Monomeric Triphosphinoboranes: Intramolecular Lewis Acid–Base Interactions between Boron and Phosphorus Atoms// INORGANIC CHEMISTRY -Vol. 61,iss. 10 (2022), s.4361-4370
- DOI:
- Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1021/acs.inorgchem.1c03618
- Źródła finansowania:
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- IDUB
- Weryfikacja:
- Politechnika Gdańska
wyświetlono 135 razy