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

Anticipated structures of homoleptic, diamagnetic polyphosphorus cations 19+, 20+ and 21+.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig5: Anticipated structures of homoleptic, diamagnetic polyphosphorus cations 19+, 20+ and 21+.

Mentions: For decades the investigation of homoleptic polyphosphorus cations was limited to mass spectroscopy29 and quantum chemical calculation30 in the gas phase. Homoleptic Pn+ cations are paramagnetic if the number of P atoms n is even. In the case of an odd number of P atoms the respective cation is diamagnetic. In general, the paramagnetic series of polyphosphorus cations is less stable. In the odd-membered series, the smaller Pn+ cations 19+ (n = 5) and 20+ (n = 7) may be described as electron-deficient Wade clusters whereas larger Pn+-cages (n ≥ 9) feature electron-precise Zintl-type structures. According to Wade's rules, a square pyramidal structure is anticipated for cation 19+ (Fig. 5, nido-cluster). Such a structure was confirmed as the most stable isomer by means of quantum chemical calculations.30a The structural motif of the second most stable isomer 19′+ (34.7 kcal mol–1 higher in energy) does not follow Wade's rules and shows a di-coordinated P atom. The most stable isomer of P7+-cage 20+ is a tricapped trigonal prism that is missing two of the capping vertices (arachno-cluster). A second isomer, which is only slightly higher in energy (20′+, 2.0 kcal mol–1), shows the P5-cage motif of 19′+ and a three-membered P ring which are both fused by a bridging phosphonium moiety. The P9+-cage 21+, which is composed of two P4-moieties fused by a phosphonium moiety, is one of the most stable homoleptic polyphosphorus cations according to quantum chemical calculations (Fig. 5).30b


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

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

Anticipated structures of homoleptic, diamagnetic polyphosphorus cations 19+, 20+ and 21+.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig5: Anticipated structures of homoleptic, diamagnetic polyphosphorus cations 19+, 20+ and 21+.
Mentions: For decades the investigation of homoleptic polyphosphorus cations was limited to mass spectroscopy29 and quantum chemical calculation30 in the gas phase. Homoleptic Pn+ cations are paramagnetic if the number of P atoms n is even. In the case of an odd number of P atoms the respective cation is diamagnetic. In general, the paramagnetic series of polyphosphorus cations is less stable. In the odd-membered series, the smaller Pn+ cations 19+ (n = 5) and 20+ (n = 7) may be described as electron-deficient Wade clusters whereas larger Pn+-cages (n ≥ 9) feature electron-precise Zintl-type structures. According to Wade's rules, a square pyramidal structure is anticipated for cation 19+ (Fig. 5, nido-cluster). Such a structure was confirmed as the most stable isomer by means of quantum chemical calculations.30a The structural motif of the second most stable isomer 19′+ (34.7 kcal mol–1 higher in energy) does not follow Wade's rules and shows a di-coordinated P atom. The most stable isomer of P7+-cage 20+ is a tricapped trigonal prism that is missing two of the capping vertices (arachno-cluster). A second isomer, which is only slightly higher in energy (20′+, 2.0 kcal mol–1), shows the P5-cage motif of 19′+ and a three-membered P ring which are both fused by a bridging phosphonium moiety. The P9+-cage 21+, which is composed of two P4-moieties fused by a phosphonium moiety, is one of the most stable homoleptic polyphosphorus cations according to quantum chemical calculations (Fig. 5).30b

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