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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

Preparation of P5+-cage cation 51+ from P4, GaCl3 and chlorophosphane 48 (top) and preparation of zwitterionic P5-cage compound 53 from P4 and zwitterionic phosphenium ion 52.
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sch14: Preparation of P5+-cage cation 51+ from P4, GaCl3 and chlorophosphane 48 (top) and preparation of zwitterionic P5-cage compound 53 from P4 and zwitterionic phosphenium ion 52.

Mentions: Other cyclic, four-membered phosphorus containing heterocycles can be employed in reactions with P4 as well.59 The cyclic chlorophosphane 48, featuring a SiCl2-backbone,60 reacts with GaCl3 to give the corresponding Lewis acid–base adduct 49 (Scheme 14). The formation of related phosphenium ion 50+ is observed only upon addition of a second equivalent of GaCl3. This can be explained by the suppression of detrimental concentrations of nucleophilic chloride anions through the formation of Ga2Cl7–.


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

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

Preparation of P5+-cage cation 51+ from P4, GaCl3 and chlorophosphane 48 (top) and preparation of zwitterionic P5-cage compound 53 from P4 and zwitterionic phosphenium ion 52.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch14: Preparation of P5+-cage cation 51+ from P4, GaCl3 and chlorophosphane 48 (top) and preparation of zwitterionic P5-cage compound 53 from P4 and zwitterionic phosphenium ion 52.
Mentions: Other cyclic, four-membered phosphorus containing heterocycles can be employed in reactions with P4 as well.59 The cyclic chlorophosphane 48, featuring a SiCl2-backbone,60 reacts with GaCl3 to give the corresponding Lewis acid–base adduct 49 (Scheme 14). The formation of related phosphenium ion 50+ is observed only upon addition of a second equivalent of GaCl3. This can be explained by the suppression of detrimental concentrations of nucleophilic chloride anions through the formation of Ga2Cl7–.

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