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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

Family of cationic polyphosphorus-chalcogen cages formally derived from stepwise isolobal exchange of [Ch] by [R2P]+ units in P4Ch3 (Ch = Se, S, left), their 31P NMR shifts versus the number of chalcogen atoms (n, middle) and the assignment of P or Ch atoms to the positions of a nortricyclane-type cage (right).
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fig13: Family of cationic polyphosphorus-chalcogen cages formally derived from stepwise isolobal exchange of [Ch] by [R2P]+ units in P4Ch3 (Ch = Se, S, left), their 31P NMR shifts versus the number of chalcogen atoms (n, middle) and the assignment of P or Ch atoms to the positions of a nortricyclane-type cage (right).

Mentions: A similar reactivity was observed for reactions of the P5+-cage 36a+ or the P73+-cage 433+ with elemental α-S8.49 The polyphosphorus cation 433+ and cationic polyphosphorus-chalcogen cages 612+ and 59f+ are formally derived from the stepwise isolobal exchange of [Se] atoms by [Ph2P]+ units in the bridging positions of the nortricyclane-type structure of P4Se3. This allows for an in-depth study of the 31P NMR characteristics of the whole series of compounds and a correlation with the observed structural features in the solid state. Fig. 13 shows the dependence of the chemical shifts of 433+, 612+ and 59f+, the related sulfur-containing cages 62a+ and 632+, and P4Ch3 (Ch = Se, S)63 on the number of chalcogen atoms in the corresponding molecules. The stepwise exchange of tetra-coordinated P atoms in 433+ by Se or S atoms is accompanied by a high-field shift of the resonances of the P atoms of the basal three-membered ring. The chemical shifts of basal P atoms in nortricyclane-type cages are influenced by the exocyclic angles of the P3-ring.63 The observed high-field shift correlates well with decreasing exocyclic angles observed in the solid state structures of the respective compounds. The resonances of apical P atoms exhibit the widest range of chemical shifts and reveal a stepwise down-field shift upon the substitution of tetra-coordinated P atoms by chalcogen atoms. This is consistent with different electronegativities of directly bonded phosphorus or chalcogen atoms. Moreover, apical P atoms show a high dependency of their chemical shift on elongation or compression of the nortricyclane framework.64 Elongation is accompanied by a decrease in the P–P–P angles involving the apical P atom. This increases the s-orbital contribution to the lone pair of electrons and leads to an upfield shift of the corresponding resonance in the 31P NMR spectrum.65 On this basis, the observed downfield shift indicates a stepwise elongation of the cages which is observed in the respective molecular structures in the solid state.


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

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

Family of cationic polyphosphorus-chalcogen cages formally derived from stepwise isolobal exchange of [Ch] by [R2P]+ units in P4Ch3 (Ch = Se, S, left), their 31P NMR shifts versus the number of chalcogen atoms (n, middle) and the assignment of P or Ch atoms to the positions of a nortricyclane-type cage (right).
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig13: Family of cationic polyphosphorus-chalcogen cages formally derived from stepwise isolobal exchange of [Ch] by [R2P]+ units in P4Ch3 (Ch = Se, S, left), their 31P NMR shifts versus the number of chalcogen atoms (n, middle) and the assignment of P or Ch atoms to the positions of a nortricyclane-type cage (right).
Mentions: A similar reactivity was observed for reactions of the P5+-cage 36a+ or the P73+-cage 433+ with elemental α-S8.49 The polyphosphorus cation 433+ and cationic polyphosphorus-chalcogen cages 612+ and 59f+ are formally derived from the stepwise isolobal exchange of [Se] atoms by [Ph2P]+ units in the bridging positions of the nortricyclane-type structure of P4Se3. This allows for an in-depth study of the 31P NMR characteristics of the whole series of compounds and a correlation with the observed structural features in the solid state. Fig. 13 shows the dependence of the chemical shifts of 433+, 612+ and 59f+, the related sulfur-containing cages 62a+ and 632+, and P4Ch3 (Ch = Se, S)63 on the number of chalcogen atoms in the corresponding molecules. The stepwise exchange of tetra-coordinated P atoms in 433+ by Se or S atoms is accompanied by a high-field shift of the resonances of the P atoms of the basal three-membered ring. The chemical shifts of basal P atoms in nortricyclane-type cages are influenced by the exocyclic angles of the P3-ring.63 The observed high-field shift correlates well with decreasing exocyclic angles observed in the solid state structures of the respective compounds. The resonances of apical P atoms exhibit the widest range of chemical shifts and reveal a stepwise down-field shift upon the substitution of tetra-coordinated P atoms by chalcogen atoms. This is consistent with different electronegativities of directly bonded phosphorus or chalcogen atoms. Moreover, apical P atoms show a high dependency of their chemical shift on elongation or compression of the nortricyclane framework.64 Elongation is accompanied by a decrease in the P–P–P angles involving the apical P atom. This increases the s-orbital contribution to the lone pair of electrons and leads to an upfield shift of the corresponding resonance in the 31P NMR spectrum.65 On this basis, the observed downfield shift indicates a stepwise elongation of the cages which is observed in the respective molecular structures in the solid state.

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