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Upstream product

• 78129-68-7 2,2-dimethylpropylidynephosphine 
• 173166-52-4 2,4,6-tri-tert-butyl-1,3,5-triphosphinine 

Relevant academic research and scientific papers

Differing reactivities of PCMe and PCBut towards a triphosphabenzene and a tetraphosphabarrelene: Synthesis of new phosphaalkyne pentamers (P5C5MenBut5-n, n = 0, 1 or 2)

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.

The phosphaalkyne cyclotetramer system - Syntheses, valence isomerizations, and reactions

In contrast to their all-carbon analogues, phosphaalkyne cyclooligomers only became accessible a few years ago. A milestone in the chemistry of cyclotetramers was the synthesis and structural characterization of the tetraphosphacubane 5, obtained as a thermolysis product of tert-butylphosphaacetylene (1). Since then, the construction of eleven cyclotetramers has been achieved, covering seven different frameworks (A-G). As a consequence of the use of kinetically stabilized phosphaalkynes as starting materials, all known cyclotetramers bear sterically demanding substituents (tert-butyl, terf-pentyl, 1-adamantyl). Cyclotetramerizations are not only achieved by thermolysis of 1, but also by alternative and selective routes such as transition-metal-mediated, Lewis acid- and base-induced processes, as well as by cycloadditions to phosphaalkyne cyclotrimers. Interestingly, these tetramers can be interconverted by various valence isomerizations. The results of thermal and photochemically-induced rearrangements are in good agreement with MO calculations carried out for the parent compounds. Phosphaalkyne cyclotetramers exhibit a highly interesting reactivity and other peculiar features. One outstanding example is the tetraphosphacubane 5, which shows unusual structural and spectroscopic properties as a result of its unique bonding arrangement. VCH Verlagsgesellschaft mbH.

η8-cyglooctatetraene metal complexes, a new class of templates for phosphaalkyne cyclooligomerizations

For the first time selective cyclodi-, tri-, and tetramerization of phosphaalkynes are induced by an unique class of transition metal complexes by changing the reaction conditions.

1,3,5,7-Tetraphosphabarrelen, ein neues cyclisches Tetramer der Phosphaalkine

Stichworte: Cyclisierungen * Oligomerisierungen * Phosphaalkine * Tetraphosphabarrelen * Zirconiumverbindungen

Selektive Synthesen von 1,3-Diphosphacyclobutadien, Dewar-1,3,5-Triphosphabenzol, 1,3,5-Triphosphabenzol und 1,3,5,7-Tetraphosphabarrelen durch Cyclooligomerisierung von Phosphaalkinen

Keywords: Cyclooligomerisierungen, Hafniumverbindungen, Heterocyclen, Phosphaalkine, Phosphoverbindungen