Unsymmetrisch diphosphorsubstituierte Acetylene

Abstract

Bis[bis(diethylamino)difluorphosphoranyl]acetylen, 4, bildet mit der äquimolaren Menge BF3 · Ether das nur bei niedrigen Temperaturen stabile Phosphonium‐tetrafluoroborat 7, das durch seine NMR‐Spektren und die Ergebnisse einer Röntgenstrukturanalyse charakterisiert wird. Mit der doppelt molaren Menge BF3 · Ether bildet 4 das Diphosphonium‐bis(tetrafluoroborat) 8. Bis[bis(diethylamino)phosphanyl]acetylen wird von Tetrachlor‐o‐benzochinon zu Verbindung 6 oxidiert.

Reactions of α-Diketones ando-Quinones with Phosphorus Compounds

“…Similarly, diphosphorus-substituted acetylene 629 is oxidized at the two phosphorus atoms with o -chloranil in diethyl ether solution at −80 °C to form acetylenebis(tetrachlorobenzodiaminodioxaphospholane) 630 in 99.7% yield …”

“…411 Similarly, diphosphorus-substituted acetylene 629 is oxidized at the two phosphorus atoms with ochloranil in diethyl ether solution at -80 °C to form acetylenebis(tetrachlorobenzodiaminodioxaphospholane) 630 in 99.7% yield. 412 The lone pair of electrons at the phosphorus center in 1σ 4 ,3σ 2 -diphosphaallene 631 can be used for a formal [1 + 4]-cycloaddition with tetrachloro-o-benzoquinone to afford the carbodiphosphorane 632, which is isolated in 62% yield. 413 Hexafluorobiacetyl reacts with the substituted mixed anhydrides of phosphorus 633 (R ) Me, Et), containing two phosphorus atoms of different coordinated number (λ 3 P, λ 4 P), in methylene chloride at -78 °C to form the oxyphosphorane anhydrides 634 414 with λ 5 P-O-λ 4 P, which are assumed to have the trigonal bipyramidal geometry about λ 5 P by analogy with other related oxyphosphoranes.…”