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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

Substitution of the phosphoniumyl-moiety of 8+ by Lewis-bases.
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sch2: Substitution of the phosphoniumyl-moiety of 8+ by Lewis-bases.

Mentions: Two mechanisms for the formation of 8+ are conceivable. Firstly, Ph2PCl reacts with GaCl3 as a halide abstracting agent giving a transient Ph2P+-phosphenium ion. This reacts with the second equivalent of Ph2PCl yielding 8+. The second and in the author's opinion more likely mechanism proceeds via the zwitterionic intermediate 9 which features a Ph2PCl molecule donating electron density from its lone pair of electrons to the lobes of the antibonding σ*(P–Cl) orbital of a second molecule of Ph2PCl. Subsequently, chloride abstraction by GaCl3 yields 8+ without an intermediary formation of a free Ph2P+-phosphenium ion. The phosphoniumyl-moiety in 8+ is easily substituted when 8+ is reacted with phosphanes of higher basicity than the leaving group.1 This is illustrated by the reaction of 8+ with Ph3P yielding 10+ and Ph2PCl (Scheme 2, left).23 Other Lewis bases are also suitable as nucleophiles. This is illustrated by the reaction of 8+ with 1,3-di-iso-propyl-4,5-dimethylimidazol-2-ylidene (L3) which yields the imidazoliumyl-substituted phosphane 11+.23


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

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

Substitution of the phosphoniumyl-moiety of 8+ by Lewis-bases.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch2: Substitution of the phosphoniumyl-moiety of 8+ by Lewis-bases.
Mentions: Two mechanisms for the formation of 8+ are conceivable. Firstly, Ph2PCl reacts with GaCl3 as a halide abstracting agent giving a transient Ph2P+-phosphenium ion. This reacts with the second equivalent of Ph2PCl yielding 8+. The second and in the author's opinion more likely mechanism proceeds via the zwitterionic intermediate 9 which features a Ph2PCl molecule donating electron density from its lone pair of electrons to the lobes of the antibonding σ*(P–Cl) orbital of a second molecule of Ph2PCl. Subsequently, chloride abstraction by GaCl3 yields 8+ without an intermediary formation of a free Ph2P+-phosphenium ion. The phosphoniumyl-moiety in 8+ is easily substituted when 8+ is reacted with phosphanes of higher basicity than the leaving group.1 This is illustrated by the reaction of 8+ with Ph3P yielding 10+ and Ph2PCl (Scheme 2, left).23 Other Lewis bases are also suitable as nucleophiles. This is illustrated by the reaction of 8+ with 1,3-di-iso-propyl-4,5-dimethylimidazol-2-ylidene (L3) which yields the imidazoliumyl-substituted phosphane 11+.23

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