Limits...
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

Reaction of R2NPCl2 (R = Cy, i-Pr) with GaCl3 and P4 and equilibrium of 34a,b+ with 33a,b+ and P4 (middle) and molecular structure of 33a[GaCl4] (left) and 34a+ (right).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC4288811&req=5

sch9: Reaction of R2NPCl2 (R = Cy, i-Pr) with GaCl3 and P4 and equilibrium of 34a,b+ with 33a,b+ and P4 (middle) and molecular structure of 33a[GaCl4] (left) and 34a+ (right).

Mentions: Employing dichlorophosphanes R2NPCl2 (R = Cy, i-Pr) in combination with GaCl3 in reactions with P4 gave distinct results. In mixtures of R2NPCl2 (R = Cy, i-Pr) and GaCl3 the corresponding phosphenium ions 33a,b+ are the only observable species.20a Indicative of their formation is a resonance in the 31P NMR which is shifted to remarkable low field.18 It is highly influenced by the nature of the respective anion (compare 33a[GaCl4]: δ = 310 ppm, 33a[Ga2Cl7]: δ = 350 ppm). The GaCl4– salt of 33a+ can be isolated and constitutes a rare example of a structurally characterized mono-amino substituted phosphenium ion (Scheme 9). Upon reacting phosphenium ions 33a,b+ with P4 insertion into a P–P bond is observed giving the CS-symmetric RP5Cl+-cage cations 34a,b+. However, these cages are in equilibrium with the respective free phosphenium ions and P4 which hampers the isolation of pure compounds 34a,b[GaCl4]. The observation of an equilibrium can be attributed to the relative stability of free 33a,b+. A similar reversibility of the phosphenium ion insertion was observed in the case of RP5Cl+ compounds. The addition of coordinating solvents like acetonitrile to solutions of 32[ECl4] (E = Ga, Al) decomposes the respective metallate anion via chloride liberation. Nucleophilic attack of free chloride anions on 32+ yields mainly the starting materials P4 and RPCl2 (R = alkyl, aryl) in a back reaction.


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

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

Reaction of R2NPCl2 (R = Cy, i-Pr) with GaCl3 and P4 and equilibrium of 34a,b+ with 33a,b+ and P4 (middle) and molecular structure of 33a[GaCl4] (left) and 34a+ (right).
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch9: Reaction of R2NPCl2 (R = Cy, i-Pr) with GaCl3 and P4 and equilibrium of 34a,b+ with 33a,b+ and P4 (middle) and molecular structure of 33a[GaCl4] (left) and 34a+ (right).
Mentions: Employing dichlorophosphanes R2NPCl2 (R = Cy, i-Pr) in combination with GaCl3 in reactions with P4 gave distinct results. In mixtures of R2NPCl2 (R = Cy, i-Pr) and GaCl3 the corresponding phosphenium ions 33a,b+ are the only observable species.20a Indicative of their formation is a resonance in the 31P NMR which is shifted to remarkable low field.18 It is highly influenced by the nature of the respective anion (compare 33a[GaCl4]: δ = 310 ppm, 33a[Ga2Cl7]: δ = 350 ppm). The GaCl4– salt of 33a+ can be isolated and constitutes a rare example of a structurally characterized mono-amino substituted phosphenium ion (Scheme 9). Upon reacting phosphenium ions 33a,b+ with P4 insertion into a P–P bond is observed giving the CS-symmetric RP5Cl+-cage cations 34a,b+. However, these cages are in equilibrium with the respective free phosphenium ions and P4 which hampers the isolation of pure compounds 34a,b[GaCl4]. The observation of an equilibrium can be attributed to the relative stability of free 33a,b+. A similar reversibility of the phosphenium ion insertion was observed in the case of RP5Cl+ compounds. The addition of coordinating solvents like acetonitrile to solutions of 32[ECl4] (E = Ga, Al) decomposes the respective metallate anion via chloride liberation. Nucleophilic attack of free chloride anions on 32+ yields mainly the starting materials P4 and RPCl2 (R = alkyl, aryl) in a back reaction.

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