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

Definition of the HCl- and HR-hemisphere in cations 32a–h+. The tetra-coordinated and the adjacent P atoms span a plane. The tri-coordinated P atom above the plane is within the HCl-hemisphere, and the P atom below the plane is in the HR-hemisphere.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig9: Definition of the HCl- and HR-hemisphere in cations 32a–h+. The tetra-coordinated and the adjacent P atoms span a plane. The tri-coordinated P atom above the plane is within the HCl-hemisphere, and the P atom below the plane is in the HR-hemisphere.

Mentions: All compounds are obtained in almost quantitative yield and high purity. In contrast to the halogen-substituted species 26a–c[A], they are stable in the solid state or when dissolved in non-coordinating solvents at ambient temperature.36,37 The cations 32a–h+ show characteristic 31P NMR spectra. Iterative line shape analysis of the observed spin systems gave chemical shifts and coupling constants in accordance with CS symmetric RP5Cl+-cages with four chemically non-equivalent phosphorus nuclei. All cages possess a mirror plane which includes the tetra-coordinated P atom and both P atoms opposing the former. Due to the reduced symmetry compared to the C2V-symmetric P5X2+-cages 26a–c+ an ABM2X spin system is observed for 32a–d+ and an ABMX2 spin system for 32e–h+. Due to the similar geometry of the P5+-core in all cations, the respective 1J(PP) and 2J(PP) coupling constants deviate only marginally. However, the chemical shifts are strongly dependent on the substituent R attached to the RP5Cl+-cage (Fig. 8). The PA and PB atoms exhibit characteristic low field resonances at approximately –275 ppm. The assignment of the A and B part to the respective P nuclei is based on the observed coupling pattern. First, the non-symmetrically substituted P5+-cage is divided by a plane spanned by the tetra-coordinated and both adjacent P atoms into a HCl- and HR-hemisphere (Fig. 9).


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

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

Definition of the HCl- and HR-hemisphere in cations 32a–h+. The tetra-coordinated and the adjacent P atoms span a plane. The tri-coordinated P atom above the plane is within the HCl-hemisphere, and the P atom below the plane is in the HR-hemisphere.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig9: Definition of the HCl- and HR-hemisphere in cations 32a–h+. The tetra-coordinated and the adjacent P atoms span a plane. The tri-coordinated P atom above the plane is within the HCl-hemisphere, and the P atom below the plane is in the HR-hemisphere.
Mentions: All compounds are obtained in almost quantitative yield and high purity. In contrast to the halogen-substituted species 26a–c[A], they are stable in the solid state or when dissolved in non-coordinating solvents at ambient temperature.36,37 The cations 32a–h+ show characteristic 31P NMR spectra. Iterative line shape analysis of the observed spin systems gave chemical shifts and coupling constants in accordance with CS symmetric RP5Cl+-cages with four chemically non-equivalent phosphorus nuclei. All cages possess a mirror plane which includes the tetra-coordinated P atom and both P atoms opposing the former. Due to the reduced symmetry compared to the C2V-symmetric P5X2+-cages 26a–c+ an ABM2X spin system is observed for 32a–d+ and an ABMX2 spin system for 32e–h+. Due to the similar geometry of the P5+-core in all cations, the respective 1J(PP) and 2J(PP) coupling constants deviate only marginally. However, the chemical shifts are strongly dependent on the substituent R attached to the RP5Cl+-cage (Fig. 8). The PA and PB atoms exhibit characteristic low field resonances at approximately –275 ppm. The assignment of the A and B part to the respective P nuclei is based on the observed coupling pattern. First, the non-symmetrically substituted P5+-cage is divided by a plane spanned by the tetra-coordinated and both adjacent P atoms into a HCl- and HR-hemisphere (Fig. 9).

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