Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis, Crystallographic Characterization and Reactivity of a Phosphinine‐B(C 6 F 5 ) 3 Lewis Pair

Lin, Jinxiong; Wossidlo., Friedrich; Coles, Nathan T.; Weber, Manuela; Steinhauer, Simon; Böttcher, Tobias; Müller, Christian

Abstract

A phosphinine-borane adduct of a Me3Si-functionalized phosphinine and the Lewis acid B(C6F5)3 has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B2H6 with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct (6-B(C6F5)3) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me3Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts.

Citation

Lin, J., Wossidlo., F., Coles, N. T., Weber, M., Steinhauer, S., Böttcher, T., & Müller, C. (2022). Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis, Crystallographic Characterization and Reactivity of a Phosphinine‐B(C 6 F 5 ) 3 Lewis Pair. Chemistry - A European Journal, 28(7), Article e202104135. https://doi.org/10.1002/chem.202104135

• Journal Article Type: Article
• Acceptance Date: Dec 30, 2021
• Online Publication Date: Jan 20, 2022
• Publication Date: Feb 1, 2022
• Deposit Date: Jan 28, 2022
• Publicly Available Date: Feb 1, 2022
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 28
• Issue: 7
• Article Number: e202104135
• DOI: https://doi.org/10.1002/chem.202104135
• Keywords: General Chemistry; Catalysis; Organic Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/7344544
• Publisher URL: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202104135