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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We prepared new thioether-arylphosphines bearing alkyl and fluoroalkyl chains at the sulfur atom in order to use them in metal-catalyzed reactions in new reaction media, such as a fluorous biphasic system. The characterization of the new compounds is discussed and the partition coefficients in the biphasic system perfluoromethylcyclohexane-cyclohexane were determined. Fluorous thioether-phosphines reacted with [Rh(acac)(CO) 2 ] under fluorous biphasic conditions to produce rhodium species retained in the fluorous phase with £2.32 ppm of rhodium loss in the organic phase. The effect of S-ponytails on the coordination properties of the new phosphines and their relation with 31 P NMR chemical shifts were supported by DFT calculations.

Di‐π‐methane rearrangement in a phosphorus compound The present manuscript reports on the synthesis of the first pyridyl‐functionalized 1‐phosphabarrelene from the corresponding heteroaromatic phosphinine and hexafluoro‐2‐butyne. This P,N‐hybrid ligand readily forms coordination compounds with RhI, W0, and Fe0 and undergoes a rather selective photochemical di‐π‐methane rearrangement in the coordination sphere of the metal center to afford a novel 5‐phosphasemibullvalene derivative. DFT calculations provide first insights into the mechanism of this reaction. More information can be found in the Full Paper by C. Müller et al. on page 14332.

Recent Developments in the Chemistry of Pyridyl-Functionalized, Low-Coordinate Phosphorus Heterocycles -[53 refs. + subrefs.]. -(MUELLER*, C.; SKLORZ, J. A. W.; DE KROM, I.; LOIBL, A.; HABICHT, M.; BRUCE, M.; PFEIFER, G.; WIECKO, J.; Chem. Lett. 43 (2014) 9, 1390-1404, http://dx.