Synthesis and Molecular Structure of Mesocyclic 3,7-Dimethyl-1,1,5,5-tetraphenyl-1λ5,5λ5-diphosphocin, a 1,5-Bis(λ5-phospha)cyclooctatetraene

Hubert Schmidbaur, Siegfried F. Gamper

Research output: Contribution to journalArticlepeer-review

6 Scopus citations


Cyclization of 1,1-bis [(diphenylphosphino)methyl]ethene (1) with 3-chloro-2-(chloromethyl)-1-propene results in the formation of the 3,7-dimethylene-1,1,5,5-tetraphenyl-1,5-diphosphocanium dichloride (2). The cyclic bis(ylide) was obtained upon double deprotonation with strong base and undergoes a double exo-endo proton-transfer rearrangement to give the title compound 3,7-dimethyl-1,1,5,5-tetraphenyl-1λ5,5λ5-diphosphocin (3). Both 2 and 3 have been characterized on the basis of 1H, 13C{1H}, and 31P{1H} NMR spectra, mass spectrometry, and elemental analysis. Orange-yellow crystals of composition 3·0.5Et2O grown from diethyl ether at −25 °C have been studied by X-ray crystallography: space group C2/c, a = 25.003 (4) Å, b = 16.773 (1) Å, c = 15.614 (2) Å, β = 116.781 (6)°, V = 5845.74 Å3, Z = 8. The mesocycle shows a puckered tublike conformation with two conjugatively isolated methallylic fragments connected via the two λ5-phosphorus atoms, which act as barriers against full π-electron delocalization, owing to the nodal planes of their d functions.

Original languageEnglish
Pages (from-to)986-989
Number of pages4
Issue number2
StatePublished - 1 Feb 1992
Externally publishedYes


Dive into the research topics of 'Synthesis and Molecular Structure of Mesocyclic 3,7-Dimethyl-1,1,5,5-tetraphenyl-1λ5,5λ5-diphosphocin, a 1,5-Bis(λ5-phospha)cyclooctatetraene'. Together they form a unique fingerprint.

Cite this