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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

Phosphanylphosphonium ion derivatives 27+–29+ and Lewis acid–base adduct 30 (classical) and 30′ (non-classical); R = alkyl, aryl.
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fig6: Phosphanylphosphonium ion derivatives 27+–29+ and Lewis acid–base adduct 30 (classical) and 30′ (non-classical); R = alkyl, aryl.

Mentions: A versatile approach to cationic polyphosphorus cages featuring alkyl- and aryl-groups represents the utilization of dichlorophosphanes RPCl2 (R = alkyl, aryl) instead of PX3 (X = I, Br, Cl).39 Mixtures of dichlorophosphanes RPCl2 and a strong Lewis acid (GaCl3, AlCl3) as a halide abstracting reagent can be utilized as the source for the phosphenium ion RPCl+. In the presence of P4, insertion into one of the P–P bonds takes place, giving access to a series of RP5Cl+-cages featuring distinct substituents R.39 Mixtures of dichlorophosphanes and AlCl3 were previously utilized for the in situ formation of phosphenium ion salts [RPCl][AlCl4] and subsequent syntheses of various phosphorus heterocycles.40 However, neither free phosphenium ions nor respective phosphenium ion sources could be verified. In some cases, the formation of Lewis acid–base complexes of the type mRPCl2·nAlCl3 (n = 1, 2; m = 1, 2) was suggested.41 Detailed investigations of mixtures of mono- and dichlorophosphanes in the presence of Lewis acids revealed the formation of chlorophosphanylchlorophosphonium ions of type 27+ (Fig. 6).42 In most cases, characteristic 1J(PP) coupling constants were observed by 31P NMR spectroscopy at ambient temperature.


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

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

Phosphanylphosphonium ion derivatives 27+–29+ and Lewis acid–base adduct 30 (classical) and 30′ (non-classical); R = alkyl, aryl.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig6: Phosphanylphosphonium ion derivatives 27+–29+ and Lewis acid–base adduct 30 (classical) and 30′ (non-classical); R = alkyl, aryl.
Mentions: A versatile approach to cationic polyphosphorus cages featuring alkyl- and aryl-groups represents the utilization of dichlorophosphanes RPCl2 (R = alkyl, aryl) instead of PX3 (X = I, Br, Cl).39 Mixtures of dichlorophosphanes RPCl2 and a strong Lewis acid (GaCl3, AlCl3) as a halide abstracting reagent can be utilized as the source for the phosphenium ion RPCl+. In the presence of P4, insertion into one of the P–P bonds takes place, giving access to a series of RP5Cl+-cages featuring distinct substituents R.39 Mixtures of dichlorophosphanes and AlCl3 were previously utilized for the in situ formation of phosphenium ion salts [RPCl][AlCl4] and subsequent syntheses of various phosphorus heterocycles.40 However, neither free phosphenium ions nor respective phosphenium ion sources could be verified. In some cases, the formation of Lewis acid–base complexes of the type mRPCl2·nAlCl3 (n = 1, 2; m = 1, 2) was suggested.41 Detailed investigations of mixtures of mono- and dichlorophosphanes in the presence of Lewis acids revealed the formation of chlorophosphanylchlorophosphonium ions of type 27+ (Fig. 6).42 In most cases, characteristic 1J(PP) coupling constants were observed by 31P NMR spectroscopy at ambient temperature.

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