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 P4 and NO[A] yielding P4NO+-cage 24[A] and subsequent reaction with P4 yielding P9+-cage compound 21[A]; A = Al(OC(CF3)3)4.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch6: Reaction of P4 and NO[A] yielding P4NO+-cage 24[A] and subsequent reaction with P4 yielding P9+-cage compound 21[A]; A = Al(OC(CF3)3)4.

Mentions: Krossing and co-workers were the first to report evidence for the existence of homoleptic polyphosphorus cations in the condensed phase.31 The attempted oxidation of P4 with I2 or Br2 in the presence of Ag(CH2Cl2)[A] (A = Al(OC(CF3)3)4) was suggested to proceed via the intermediary formation of P5+-cage cation 19+ (Scheme 5).32 However, cation 19+ is highly reactive and reacts with the solvent to give phosphonium ion 22+ as one of the main products. Cation 22+ forms via elimination of P4 and two-fold insertion into C–Cl bonds of CDCl3 molecules which was used as solvent. In the case of I2 as oxidant, P4 reacts partially to give PI3 which was suggested to react with intermediate 19+ to give P4 and the bis(phosphanyl)-substituted phosphonium ion 23+. Experimental evidence confirming the presence of 19+ in the reaction mixtures was not obtained; however, the suggested reaction pathways are in accordance with quantum chemical calculations.32 The nitrosonium salt [NO][A] (A = Al(OC(CF3)3)4) was also investigated as a possible one electron oxidant. However, the reaction of P4 with [NO][A] yields P4NO+-cage compound 24[A] via insertion of the nitrosonium cation into a P–P bond (Scheme 6).33


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

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

Reaction of P4 and NO[A] yielding P4NO+-cage 24[A] and subsequent reaction with P4 yielding P9+-cage compound 21[A]; A = Al(OC(CF3)3)4.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch6: Reaction of P4 and NO[A] yielding P4NO+-cage 24[A] and subsequent reaction with P4 yielding P9+-cage compound 21[A]; A = Al(OC(CF3)3)4.
Mentions: Krossing and co-workers were the first to report evidence for the existence of homoleptic polyphosphorus cations in the condensed phase.31 The attempted oxidation of P4 with I2 or Br2 in the presence of Ag(CH2Cl2)[A] (A = Al(OC(CF3)3)4) was suggested to proceed via the intermediary formation of P5+-cage cation 19+ (Scheme 5).32 However, cation 19+ is highly reactive and reacts with the solvent to give phosphonium ion 22+ as one of the main products. Cation 22+ forms via elimination of P4 and two-fold insertion into C–Cl bonds of CDCl3 molecules which was used as solvent. In the case of I2 as oxidant, P4 reacts partially to give PI3 which was suggested to react with intermediate 19+ to give P4 and the bis(phosphanyl)-substituted phosphonium ion 23+. Experimental evidence confirming the presence of 19+ in the reaction mixtures was not obtained; however, the suggested reaction pathways are in accordance with quantum chemical calculations.32 The nitrosonium salt [NO][A] (A = Al(OC(CF3)3)4) was also investigated as a possible one electron oxidant. However, the reaction of P4 with [NO][A] yields P4NO+-cage compound 24[A] via insertion of the nitrosonium cation into a P–P bond (Scheme 6).33

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