This highlight review provides an overview of recent developments in the chemistry of pyridyl-functionalized λ 3 σ 2 -phosphinines and 3H-1,2,3,4-triazaphospholes. The access to novel chelating, low-coordinate phosphorus heterocycles can lead to a much broader scope for potential applications. New developments in areas such as homogeneous catalysis, molecular materials, and supramolecular chemistry can consequently be foreseen in the near future.
The λ 3 -phosphinine derivatives 2,6-diphenyl-4-(p-tolyl)phosphinine and 2-(2Ј-pyridyl)-4,6-diphenylphosphinine were quantitatively converted into the corresponding λ 4 -phosphinine anions by reaction with phenyllithium. Systematic hydrolysis experiments with H 2 O and MeOH show that a subtle interplay between the pK a values of the generated 1,2-dihydrophosphinine derivatives and the pK b value of the formed bases, LiOH and LiOCH 3 , respectively, leads either to the kinetic or thermodynamic product. The coordination[a]
Dedicatedtothe element phosphorus on the 350th anniversary of its discovery.Abstract: The [4+ +2] cycloaddition of 2-(2'-pyridyl)-4,6-diphenyl-l 3 -phosphinine with the highly reactive dienophile hexafluoro-2-butyne has been studied and the first pyridylfunctionalized 1-phosphabarrelenew as obtained and structurally characterized. Although monodentate CF 3 -1-phosphabarrelenes show only ap oorc oordination ability,t he chelating nature of the novel P, N-hybrid ligand gives accesst ov arious transition-metal complexes.U pon irradiation with UV light, the pyridyl-functionalized 1-phosphabarrelene undergoes ar ather selective di-p-methane rearrangementi nt he coordination sphere of the metal center, leading to the formation of ac omplex based on ah itherto unknown pyridylfunctionalized 5-phosphasemibullvalene derivative.D FT calculations provide first insights into the mechanism of this reaction.[a] Dr.M.B ruce, Dr.M .P apke,M.W eber,Prof.
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