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Monomeric Triphosphinoboranes: Intramolecular Lewis Acid–Base Interactions between Boron and Phosphorus Atoms
Abstract
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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- DOI:
- Digital Object Identifier (open in new tab) 10.1021/acs.inorgchem.1c03618
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- Category:
- Articles
- Type:
- artykuły w czasopismach
- Published in:
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INORGANIC CHEMISTRY
no. 61,
pages 4361 - 4370,
ISSN: 0020-1669 - Language:
- English
- Publication year:
- 2022
- Bibliographic description:
- 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:
- Digital Object Identifier (open in new tab) 10.1021/acs.inorgchem.1c03618
- Sources of funding:
-
- IDUB
- Verified by:
- Gdańsk University of Technology
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