A new series of 2,4,6‐triaryl‐λ5‐phosphinines have been synthesized that contain different substituents both on the carbon backbone and the phosphorus atom of the six‐membered heterocycle. Their optical and redox properties were studied in detail, supported by in‐depth theoretical calculations. The modularity of the synthetic strategy allowed the establishment of structure–property relationships for this class of compounds and an OLED based on a blue phosphinine emitter could be developed for the first time.
3H-1,2,3,4-Triazaphosphole derivatives can be selectively alkylated with Meerwein's reagent at the most nucleophilic nitrogen atom. According to the principle of valence isoelectronicity, the corresponding phosphorus heterocycle represents the first formal phosphorus analogue of the well-known 1,2,3-triazolylidenes (mesoionic carbenes). Theoretical calculations revealed that the cation in triazaphospholenium tetrafluoroborate is an aromatic system with a high degree of π-conjugation. First investigations showed that the cationic phosphorus heterocycle can stabilize a [Cu Br ] dianion by formation of a neutral coordination compound with an unusual bonding situation between phosphorus and copper(I).
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.
Arsaalkynes can undergo regioselective and quantitative [3+2] cycloaddition reactions with organic azides to give hitherto unknown 3H-1,2,3,4-triazaarsole derivatives. The reaction product was obtained as a white, air- and moisture-stable solid, and the presence of a planar, five-membered arsenic heterocycle was unambiguously verified by means of X-ray crystallography. DFT calculations gave insight into the electronic structure of these novel compounds compared to tetrazoles and triazaphospholes. The coordination chemistry towards Re(I) was investigated and compared with the structurally related phosphorus-containing ligand. These preliminary investigations pave the way for a new class of arsenic heterocycles and fill the gap between the azaarsoles already known.
A novel bis-CF3-substituted diazaphosphole was synthesized selectively from hexafluoro-2-butyne and a 3H-1,2,3,4-triazaphosphole derivative. The [4+2] cycloaddition and subsequent cycloreversion reaction under elimination of pivaloyl nitrile affords the product in high...
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