78129-68-7Relevant articles and documents
Remarkable Differences in the Reactivities of the (E)- and (Z)-Isomers of a Phospha-alkene
Barron, Andrew R.,Cowley, Alan H.,Hall, Stephen W.
, p. 980 - 981 (1987)
The (E)- and (Z)-isomers of the phospha-alkene, But(Me3SiO)C=PSiMe3, show markedly different reactivities towards heat and molecular oxygen.
Differing reactivities of PCMe and PCBut towards a triphosphabenzene and a tetraphosphabarrelene: Synthesis of new phosphaalkyne pentamers (P5C5MenBut5-n, n = 0, 1 or 2)
Jones, Cameron,Schulten, Christian,Stasch, Andreas
, p. 1929 - 1933 (2008/02/03)
The reaction of excess PCMe with the triphosphabenzene, 1,3,5-P 3C3But3, yields a phosphaalkyne pentamer, P5C5Me2But3, which displays a pentaphosphaisolumibullvalene core structure. Its treatment with [W(CO)5(THF)] gives a complex of this cage, [{W(CO) 5}2(-η1:η1-P 5C5Me2But3)], which has been structurally characterised. In contrast, the previously reported reaction of PCBut with 1,3,5-P3C3But 3, affords, in addition to the known tetraphosphabarrelene, 1,3,5,7-P4C4But4, a new phosphaalkyne pentamer (P5C5But5), which has a partially unsaturated "open cage" core. Although PCBu t does not react with 1,3,5,7-P4C4Bu t4, the reaction of PCMe with the tetraphosphabarrelene is shown to give a mixture of products. Treatment of these with [W(CO) 5(THF)] leads to the isolation of the tungsten carbonyl complex, [{W(CO)5}{W(CO)4}(-η1:η4- P5C5MeBut4)], which has been structurally characterised. This study suggests that PCMe has a significantly greater reactivity towards cycloadditions than its bulkier counterpart, PCBut. The Royal Society of Chemistry 2007.
Lewis acid mediated spirocyclotrimerization of phosphaalkynes -key step for the selective and of triphospfaa dewar benzenes
Breit, Bernhard,Regitz, Manfred
, p. 489 - 494 (2007/10/03)
In the presence of Lewis acidic derivatives of group 13 elements, phosphaalkynes 7 undergo spirocvclotrimerization with incorporation of the corresponding Lewis acids to form 10a-f. Scope and limitations of this novel cyclooligomerization process are examined. Starting from the spirocyclotrirner 10a reaction with the Lewis base dimethyl sulfoxide, we have in hand for the first time a method for the selective genera-tion of two isomeric triphospha Dewar benzene derivatives (18, 19). Both can be trapped efficiently by further reaction with the phosphaalkyne to furnish the two novel phosphaalkyne cyclotetramers 20 and 21, both still possessing a phosphorus-carbon double bond, In the case of 21, further functionalization of the phosphaalkene unit is possible by [3 + 2] cycloaddition with a nitrile oxide (→ 23). VCH Veriagsgesellschafi mbH, 1996.