Beiträge zur Chemie des Phosphors. 65. Zur Kenntnis der Cyclo‐carba‐phosphane (PC₆H₅)₄CH₂, (PC₆H₅)₄CH₂S und (PC₆H₅)₄CH₂S₂

Abstract

Bei der Reaktion von 1,2,3,4‐Tetraphenyl‐cyclo‐5‐carba‐1,2,3,4‐tetraphosphan (PC6H5)4CH2 1 mit Schwefel im Verhältnis 4 C6H5P:1 S bzw. 2 C6H5P:1 S entstehen die Thio‐cyclo‐carba‐phosphane (PC6H5)4CH2S 2 bzw. (PC6H5)4CH2S2 3. Die Schwefelatome in 2 und 3 sind exocyclisch an den der CH2‐Gruppe benachbarten Phosphoratomen gebunden, was ein Indiz für die Stabilität des P4C‐Ringgerüstes ist. Bezüglich der Phenylsubstituenten weisen 1, 2 und 3 „all‐trans”︁‐Konfiguration auf. Die 31P‐ und 1H‐NMR‐Parameter für 1 und 3 werden mitgeteilt und diskutiert.

Cage Chirality of PC Cage Compounds: Highly Diastereoselective Formation of Diastereomeric P5‐Deltacyclenes, Separation of Diastereomers, and Removal of the Chiral Auxiliary

“…Coupling along the edge of a five-membered ring is much more effective ( 1 J P1,P2 % 280 Hz) than coupling between two phosphorus atoms sharing a three-membered ring structure ( 1 J P2,P3 % 150 Hz). [12] The atoms P4 and P5 do not show 1 J P,P coupling and are differentiated by the characteristic chemical shift of sp 2 -hybridized P5. [5] Following the demands of theory, the enantiomeric mixture 8A C H T U N G T R E N N U N G (R+S) and its isolated enantiomer 8 are indistinguishable by NMR spectroscopy in achiral media.…”

Reactivity of cyclooligophosphanes: synthesis and structural characterisation of cyclo-1,4-(BH3)2(P4Ph4CH2) and cyclo-1,2-(BH3)2(P5Ph5)

“…17 This may explain why a second isomer of 2•2S was not observed by Baudler and co-workers in solution. 7 Although the solution behaviour of 3 can certainly not be regarded as trivial, the 31 P{ 1 H} NMR spectrum of 4 reveals a much more complicated situation (Fig. 5).…”

“…Interestingly, while BH 3 complexes of cyclooligophosphanes have remained elusive, Baudler et al reported reactions of the cyclooligophosphanes cyclo-(P 4 Ph 4 CH 2 ) (2) and cyclo-(P 5 Ph 5 ) (5) with elemental sulfur to give the sulfides cyclo-(S 2 P 4 Ph 4 CH 2 ) (2•2S) 7 and cyclo-(SP 4 Ph 4 ). 8 )]OTf (R, R = Me, Ph) can be prepared by reaction of cyclooligosphanes with phosphenium triflates or methyl triflate.…”

Organo–Phosphorus–Sulfur Heterocycles by Reactions of Phenylphosphine with Ketones

“…This resulted in longer reaction times and the formation of a two-phase system. 31 P-NMR spectra of the lower phase after a reaction time of 18 h revealed 5 sets of different peaks which could be attributed to the diastereomers (1a,Z)/(1b,E), compound (2) in addition to the intermediate (3a)/(3b). By comparing the coupling nature of the NMR shifts of the intermediates with those of compound (1a,Z)/(1b,E), we were able to elucidate structural information.…”