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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

Reaction of 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry (top) and molecular structure of cation 69+ (bottom).
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sch19: Reaction of 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry (top) and molecular structure of cation 69+ (bottom).

Mentions: A combination of phosphenium ion and carbene mediated P4 activation constitutes a novel, potentially versatile approach for the preparation of cationic polyphosphorus cages. This strategy allows for the preparation of polyphosphorus cations featuring imidazoliumyl-substituents. These substituents are valuable for two purposes. First, they serve well for the stabilization of cations by delocalization of the positive charge.70 Second, they stabilize low-coordinated P moieties by reducing the nucleophilicity of directly bonded P atoms.71 The reaction of P5+-cage compound 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry yields the bicyclo[1.1.0]tetraphosphane 69[GaCl4] (Scheme 19).67 The bicyclic framework is substituted with an imidazoliumyl-group in an exo-position and a phosphanyl-group in an endo-position. This is reminiscent of the intermediate 31 observed in the formation of RP5Cl+-cages. Cation 69+ features an ACEMX spin system indicating a non-symmetrical molecular structure due to hindered rotation around the P–P bond involving the Dipp-substituted P atom. The endo,exo-substitution of 69+ causes a short intermolecular distance between the Dipp- and the imidazoliumyl-substituted P atoms in the solid state (see molecular structure in Scheme 19). This spatial proximity is also indicated in solution by an extraordinarily large 3J(PP) coupling constant of 244.6 Hz in the 31P NMR spectrum.


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

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

Reaction of 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry (top) and molecular structure of cation 69+ (bottom).
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch19: Reaction of 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry (top) and molecular structure of cation 69+ (bottom).
Mentions: A combination of phosphenium ion and carbene mediated P4 activation constitutes a novel, potentially versatile approach for the preparation of cationic polyphosphorus cages. This strategy allows for the preparation of polyphosphorus cations featuring imidazoliumyl-substituents. These substituents are valuable for two purposes. First, they serve well for the stabilization of cations by delocalization of the positive charge.70 Second, they stabilize low-coordinated P moieties by reducing the nucleophilicity of directly bonded P atoms.71 The reaction of P5+-cage compound 32h[GaCl4] with carbene L7 in a 1 : 1 stoichiometry yields the bicyclo[1.1.0]tetraphosphane 69[GaCl4] (Scheme 19).67 The bicyclic framework is substituted with an imidazoliumyl-group in an exo-position and a phosphanyl-group in an endo-position. This is reminiscent of the intermediate 31 observed in the formation of RP5Cl+-cages. Cation 69+ features an ACEMX spin system indicating a non-symmetrical molecular structure due to hindered rotation around the P–P bond involving the Dipp-substituted P atom. The endo,exo-substitution of 69+ causes a short intermolecular distance between the Dipp- and the imidazoliumyl-substituted P atoms in the solid state (see molecular structure in Scheme 19). This spatial proximity is also indicated in solution by an extraordinarily large 3J(PP) coupling constant of 244.6 Hz in the 31P NMR spectrum.

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