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The chemistry of cationic polyphosphorus cages--syntheses, structure and reactivity.

Holthausen MH, Weigand JJ - Chem Soc Rev (2014)

Bottom Line: The aim of this review is to provide a comprehensive view of the chemistry of cationic polyphosphorus cages.The synthetic protocols established for their preparation, which are all based on the functionalization of P4, and their intriguing follow-up chemistry are highlighted.In addition, this review intends to foster the interest of the inorganic, organic, catalytic and material oriented chemical communities in the versatile field of polyphosphorus cage compounds.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Toronto, Toronto, Canada. m.holthausen@utoronto.ca.

ABSTRACT
The aim of this review is to provide a comprehensive view of the chemistry of cationic polyphosphorus cages. The synthetic protocols established for their preparation, which are all based on the functionalization of P4, and their intriguing follow-up chemistry are highlighted. In addition, this review intends to foster the interest of the inorganic, organic, catalytic and material oriented chemical communities in the versatile field of polyphosphorus cage compounds. In the long term, this is envisioned to contribute to the development of new synthetic procedures for the functionalization of P4 and its transformation into (organo-)phosphorus compounds and materials of added value.

No MeSH data available.


Related in: MedlinePlus

Calculated reaction pathways for the reaction of 28e[GaCl4] and P4; calculated differences of the enthalpies at 298.15 K (ΔH298) are given for the optimized structures of MP2/6-31G(d) and the optimized structures of 28e[GaCl4] + P4 were defined as 0 kcal mol–1.
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fig7: Calculated reaction pathways for the reaction of 28e[GaCl4] and P4; calculated differences of the enthalpies at 298.15 K (ΔH298) are given for the optimized structures of MP2/6-31G(d) and the optimized structures of 28e[GaCl4] + P4 were defined as 0 kcal mol–1.

Mentions: Quantum chemical calculations were carried out to determine which of the observed species serves as the phosphenium ion source in a reaction with P4. According to these results,44 the formation of RP5Cl+-cages via a free phosphenium ion RPCl+ can be excluded. Attempts to calculate a feasible reaction mechanism from adducts 30 or 30′ as sources of phosphenium ions were not successful. Thus, the reaction of P4 with methyl-substituted phosphanylphosphonium derivative 28e+ was investigated (Fig. 7). A single step insertion of the phosphenium moiety into a P–P bond of the P4 tetrahedron is viable and the calculated energy profile of the reaction path is denoted in black. In addition, a two-step reaction pathway is feasible as well (energy profile is shown in red).


The chemistry of cationic polyphosphorus cages--syntheses, structure and reactivity.

Holthausen MH, Weigand JJ - Chem Soc Rev (2014)

Calculated reaction pathways for the reaction of 28e[GaCl4] and P4; calculated differences of the enthalpies at 298.15 K (ΔH298) are given for the optimized structures of MP2/6-31G(d) and the optimized structures of 28e[GaCl4] + P4 were defined as 0 kcal mol–1.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4288811&req=5

fig7: Calculated reaction pathways for the reaction of 28e[GaCl4] and P4; calculated differences of the enthalpies at 298.15 K (ΔH298) are given for the optimized structures of MP2/6-31G(d) and the optimized structures of 28e[GaCl4] + P4 were defined as 0 kcal mol–1.
Mentions: Quantum chemical calculations were carried out to determine which of the observed species serves as the phosphenium ion source in a reaction with P4. According to these results,44 the formation of RP5Cl+-cages via a free phosphenium ion RPCl+ can be excluded. Attempts to calculate a feasible reaction mechanism from adducts 30 or 30′ as sources of phosphenium ions were not successful. Thus, the reaction of P4 with methyl-substituted phosphanylphosphonium derivative 28e+ was investigated (Fig. 7). A single step insertion of the phosphenium moiety into a P–P bond of the P4 tetrahedron is viable and the calculated energy profile of the reaction path is denoted in black. In addition, a two-step reaction pathway is feasible as well (energy profile is shown in red).

Bottom Line: The aim of this review is to provide a comprehensive view of the chemistry of cationic polyphosphorus cages.The synthetic protocols established for their preparation, which are all based on the functionalization of P4, and their intriguing follow-up chemistry are highlighted.In addition, this review intends to foster the interest of the inorganic, organic, catalytic and material oriented chemical communities in the versatile field of polyphosphorus cage compounds.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Toronto, Toronto, Canada. m.holthausen@utoronto.ca.

ABSTRACT
The aim of this review is to provide a comprehensive view of the chemistry of cationic polyphosphorus cages. The synthetic protocols established for their preparation, which are all based on the functionalization of P4, and their intriguing follow-up chemistry are highlighted. In addition, this review intends to foster the interest of the inorganic, organic, catalytic and material oriented chemical communities in the versatile field of polyphosphorus cage compounds. In the long term, this is envisioned to contribute to the development of new synthetic procedures for the functionalization of P4 and its transformation into (organo-)phosphorus compounds and materials of added value.

No MeSH data available.


Related in: MedlinePlus