Borane adducts of aromatic phosphorus heterocycles: synthesis, crystallographic characterization and reactivity of a phosphinine‐B(C6F5)3 lewis pair

Lin, Jinxiong, Wossidlo, Friedrich, Coles, Nathan T. ORCID: https://orcid.org/0000-0001-6190-9080, Weber, Manuela, Steinhauer, Simon, Böttcher, Tobias and Müller, Christian 2022. Borane adducts of aromatic phosphorus heterocycles: synthesis, crystallographic characterization and reactivity of a phosphinine‐B(C6F5)3 lewis pair. Chemistry - A European Journal 28 (7) , e202104135. 10.1002/chem.202104135

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Wiley
ISSN:	0947-6539
Date of First Compliant Deposit:	6 January 2025
Date of Acceptance:	30 December 2022
Last Modified:	06 Jan 2025 10:05
URI:	https://orca.cardiff.ac.uk/id/eprint/173587

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