121097-72-1

Upstream product

• 109613-89-0 zirconocene 1,3-diphosphabicyclo[1.1.0]butane 
• 21907-22-2 diphenylantimony trichloride 
• 78129-68-7 2,2-dimethylpropylidynephosphine 
• 117972-60-8 tert-pentylphosphaacetylene 

Relevant academic research and scientific papers

Promotion of phosphaalkyne cyclooligomerisation by a Sb(V) to Sb(III) redox process

A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[4.2.0. 02,5]octa-3,7-diene, is obtained from reaction of the zirconocene 1,3-diphosphabicyclo[1.1.0]butane with Ph2SbCl3 in THF or CH2Cl2. Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph2SbCl and 1,3-diphosphabicyclo[1.1.0]butane plays a pivotal role in the reaction. The zwitterionic character of this intermediate species allows it to act simultaneously as both an ene and an eneophile, and a symmetry-allowed bimolecular reaction leads to the tetraphosphaladderene species via a spirocyclic intermediate.

The chemistry of arsenic-carbon multiple bonds: Arsaalkenes and arsaalkynes

The present article gives an account of the synthesis and structure as well as the spectroscopic and chemical properties of arsaalkenes R1As=CR2R3 and arsaalkynes RC≡As. Arsaalkenes are significantly less stable and more reactive than the corresponding phosphaalkenes. Only one kinetically stabilized arsaalkyne has been described so far. VCH Verlagsgesellschaft mbH, 1996.

The metal-initiated cyclooligomerization of phospha-alkynes and its consequences [1]

1,3-Diphosphacyclobutadienes 4 are almost certainly intermediates in the conversion by hexachloroethane of phosphaalkyne dimer complexes 3 to the tetraphosphacubanes 5. We now describe trapping reactions of 4, generated in the same way, wilh phosphaalkyne 1 (→9), ynamines 10 (→13), and electron-poor alkynes 11 (→14). The cyclooligomerization of 1 initiated by t-Bu-N=VCl3·DME (15) leads to the azatetraphosphaquadricyclanes 20 while the reaction with the stronger Lewis acid t-Bu-N=VCl3 (21) furnishes the 1,3,5-triphosphabenzenes 23 in high selectivity.

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.

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

Organophosphorus compounds; 96. Cyclotetramerization of phosphaalkynes to 1,3,5,7-tetraphosphacubanes

Depending on the reaction conditions, small amounts of the tetraphosphapentacyclic compounds (tetraphosphacubanes) 4a, b as well as the isomeric tetraphosphatetracyclic products 5a, b can be isolated from the thermolyses of the phosphaalkynes 3a, b. This cyclotetramerization can be directed towards the formation of tetraphosphacubanes when the whole process is split into two sequential cyclodimerizations. Firstly, the zirconocene-phosphaalkyne dimer complexes 8a-d are prepared from 7 and 3a-d; in the second step, the Cp2Zr fragment is extruded from 8a-d by reaction with hexachloroethane. The tetraphosphacubanes 4a-d are obtained in good yields by this process. Only in the case of 1-adamantyl-phosphaacetylene and the penta- and tetracyclic products formed concomitantly (7 + 3e → 8e → 11 + 12). Putative intermediates for the second dimerization step are the diphosphetes 9a-e and their Diels-Alder dimers 10a-e.