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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

Stepwise insertion of selenium atoms into P–P bonds of 36a,f+ and stepwise substitution of [Ph2P]+-moieties in 433+ by selenium atoms giving the nortricyclane-type polyphosphorus-chalcogen cage cations 59a,f+ and 612+.
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sch17: Stepwise insertion of selenium atoms into P–P bonds of 36a,f+ and stepwise substitution of [Ph2P]+-moieties in 433+ by selenium atoms giving the nortricyclane-type polyphosphorus-chalcogen cage cations 59a,f+ and 612+.

Mentions: Recently, a third approach garnered interest which is based on using cationic polyphosphorus cages as starting materials for the preparation of cationic polyphosphorus-chalcogen cages. They constitute potentially versatile reagents due to the multitude of distinctly substituted derivatives which are all conveniently obtained in one step procedures from white phosphorus.49 Chalcogenation reactions of R2P5+-cage compounds 36a[GaCl4] and 36f[GaCl4] with elemental grey selenium yield the corresponding polyphosphorus-selenium cages 59a[GaCl4] and 59f[GaCl4] (Scheme 17). Both are obtained at elevated temperatures (110–150 °C) following a solvent-free protocol. In some cases, the addition of one equivalent of GaCl3 is beneficial since it lowers the melting point of the respective melt. Both cations are formed upon insertion of two selenium atoms into two P–P bonds adjacent to the phosphonium moieties in 36a,f+.


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

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

Stepwise insertion of selenium atoms into P–P bonds of 36a,f+ and stepwise substitution of [Ph2P]+-moieties in 433+ by selenium atoms giving the nortricyclane-type polyphosphorus-chalcogen cage cations 59a,f+ and 612+.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch17: Stepwise insertion of selenium atoms into P–P bonds of 36a,f+ and stepwise substitution of [Ph2P]+-moieties in 433+ by selenium atoms giving the nortricyclane-type polyphosphorus-chalcogen cage cations 59a,f+ and 612+.
Mentions: Recently, a third approach garnered interest which is based on using cationic polyphosphorus cages as starting materials for the preparation of cationic polyphosphorus-chalcogen cages. They constitute potentially versatile reagents due to the multitude of distinctly substituted derivatives which are all conveniently obtained in one step procedures from white phosphorus.49 Chalcogenation reactions of R2P5+-cage compounds 36a[GaCl4] and 36f[GaCl4] with elemental grey selenium yield the corresponding polyphosphorus-selenium cages 59a[GaCl4] and 59f[GaCl4] (Scheme 17). Both are obtained at elevated temperatures (110–150 °C) following a solvent-free protocol. In some cases, the addition of one equivalent of GaCl3 is beneficial since it lowers the melting point of the respective melt. Both cations are formed upon insertion of two selenium atoms into two P–P bonds adjacent to the phosphonium moieties in 36a,f+.

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