Synthese und Reaktivität von Phosphacyclopentadienid-Anionen
Final Report Abstract
We have found that: - 1,2,3-triphenylcyclopropenylphosphonium salts react cleanly with sodium polyphosphides to give sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide in good yield. - 1-alkyl-3,4,5-triphenyl-1,2-diphosphacylopenta-2,4-dienes can act both as diene and dienophile in cycloaddition reactions, similar to 2-H phospholes. However, in contrast to 2-H phospholes the cyclodimerization reaction of 1 occurs only under harsh reaction conditions to give the product of a [2+2] cycloaddition reaction. - 3,4,5-triphenyl-1,2-diphosphacyclopentadienide can form two types of manganese and rhenium carbonyl complexes with different coordination modes of the 1,2-diphosphacyclopentadienide ligand – bridging μ:η1,η1 like pyrazole, or terminal η5 like cyclopentadienyl ligands, which are products of kinetic or thermodynamic control of the reaction, respectively, and can be obtained separately using different reaction conditions. - The dinuclear manganese complexes containing 1,2-diphosphacyclopentadienide ligands show antiferromagnetic interaction of the manganese(II) species formed due to metal-to-ligand charge transfer.
Publications
- Bezkichko I., Miluykov V., Kataev A., Krivolapov D., Litvinov I., Sinyashin O., Hey- Hawkins E. An unusual reaction of cyclopropenylphosphonium bromide with sodium polyphosphides ¿ A novel approach to sodium 3,4,5-triphenyl-1,2- diphosphacyclopentadienide. J. Organomet. Chem., 2008, 693, 3318-3320.
- Bezkishko I.A., Miluykov V.A., Kataev V.A., Sinyashin O.G., Hey-Hawkins E. Complexing properties of 1,2-diphosphacyclopentadienyd anion. XV-th International conference on chemistry of phosphorus compounds, May 25-30, 2008, Sankt- Peterburg, Russia. Book of abstracts P.114.
- Miluykov V., Bezkishko I., Zagidullin A., Sinyashin O., Lönnecke P., Hey-Hawkins E. Cycloadddition Reactions of 1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4- dienes. Eur. J. Org. Chem. 2009, 1269-1274.
- Miluykov V., Kataev A., Sinyashin O., Hey-Hawkins E. The Chemical Properties of Alkali Metals Heptaphosphides. Phosphorus, Sulfur, and Silicon, and related Elements, 2008, 183, 509-512.
- Miluykov V.A., Bezkishko I.A., Kataev V.A., Sinyashin O.G., Hey-Hawkins E. Transition metal complexes, containing 1,2-diphosphacyclopentadienide ligand. IV International conference «Highspin molecule and molecular magnets», October 14- 19, 2008, Ekaterinburg, Russia. Book of abstracts ¿.66.
- Miluykov V.A., Kataev A.V., Sinyashin O.G., Hey-Hawkins E. Trisodium heptaphosphide in reaction witn cyclopropenyl complexes of nickel. Russia chemical bulletin, 2007, 2, 294-297.
- Miluykov V.A., Kataev V.A., Bezkishko I.A., Sinyashin O.G., Hey-Hawkins E. The synthesis and chemical properties of 1,2-diphosphacyclopentadienyd anion. XV-th International conference on chemistry of phosphorus compounds, May 25-30, 2008, Sankt-Peterburg, Russia. Book of abstracts P.59.
- Zagidullin ¿.¿., Miluykov V.A., Bezkishko I.A., Sinyashin O.G., Lonnecke P., Hey- Hawkins E. The cycloaddition reaction of 1,2-diphospholes. VIII Scientific conferences of young scientists, post-graduate students and students, Kazan state university, "Materials and technogies of XXI century", October 28-29, 2008, Kazan, Russia. Book of abstracts p. 34.
- Zagidullin ¿.¿., Miluykov V.A., Bezkishko I.A., Sinyashin O.G., Lonnecke P., Hey- Hawkins E. The cycloaddition reaction of 1,2-diphospholes. ¿¿¿¿¿¿¿¿¿¿ ¿¿¿¿¿- ¿¿¿¿¿¿¿¿¿¿¿ ¿¿ ¿¿¿¿¿¿¿¿¿¿¿¿ ¿¿¿¿¿, November 24-28, 2008, Ekaterinburg, Russia. Book of abstracts p. 47.
