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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 sequence for the carbene-induced [3+2]-fragmentation of P5+-cage 32h+.
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sch21: Reaction sequence for the carbene-induced [3+2]-fragmentation of P5+-cage 32h+.

Mentions: The P2 fragment was identified as the neutral P2 species 70 featuring an inversely-polarized68 phosphaalkene moiety. The di-coordinated P atom bears a phosphanyl-substituent which originates from the tetra-coordinated P atom of starting material 32h+. The P3 fragment was identified as GaCl4– salt of cation 71+ which features a chain of three di-coordinated P atoms terminated by two imidazoliumyl-substituents. This compound is characterized by a deep green colour that results from n → π* and π → π* transitions similar to those observed in diphosphenes.69 Quantum chemical calculations elucidated the bonding in 71+.67 The frontier orbital arrangement of the cation is closely related to the classical π-system of the C3-allyl anion. Thus, 71+ features a local triphosphaallylanion moiety substituted with imidazoliumyl-groups. The mechanism of the [3+2] fragmentation is explained by the reaction sequence in Scheme 21 on the basis of experimental evidence and quantum chemical calculations.67 The reaction of 32h+ with the first equivalent of L7 yields the experimentally verified species 69+. The nucleophilic attack of L7 occurs at a P atom adjacent to the phosphonium moiety in 32h+ and initiates a P–P bond cleavage. This reaction step is the reverse of the last step in the formation of RP5Cl+-cages (Fig. 7) and is in accordance with the observed reversibility of phosphenium ion insertion into P–P bonds of P4 (vide infra). The nucleophilic attack of a second carbene L7 occurs at the endo-substituted P atom of 69+ and initiates a P–P bond cleavage in the respective P3-ring.


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

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

Reaction sequence for the carbene-induced [3+2]-fragmentation of P5+-cage 32h+.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch21: Reaction sequence for the carbene-induced [3+2]-fragmentation of P5+-cage 32h+.
Mentions: The P2 fragment was identified as the neutral P2 species 70 featuring an inversely-polarized68 phosphaalkene moiety. The di-coordinated P atom bears a phosphanyl-substituent which originates from the tetra-coordinated P atom of starting material 32h+. The P3 fragment was identified as GaCl4– salt of cation 71+ which features a chain of three di-coordinated P atoms terminated by two imidazoliumyl-substituents. This compound is characterized by a deep green colour that results from n → π* and π → π* transitions similar to those observed in diphosphenes.69 Quantum chemical calculations elucidated the bonding in 71+.67 The frontier orbital arrangement of the cation is closely related to the classical π-system of the C3-allyl anion. Thus, 71+ features a local triphosphaallylanion moiety substituted with imidazoliumyl-groups. The mechanism of the [3+2] fragmentation is explained by the reaction sequence in Scheme 21 on the basis of experimental evidence and quantum chemical calculations.67 The reaction of 32h+ with the first equivalent of L7 yields the experimentally verified species 69+. The nucleophilic attack of L7 occurs at a P atom adjacent to the phosphonium moiety in 32h+ and initiates a P–P bond cleavage. This reaction step is the reverse of the last step in the formation of RP5Cl+-cages (Fig. 7) and is in accordance with the observed reversibility of phosphenium ion insertion into P–P bonds of P4 (vide infra). The nucleophilic attack of a second carbene L7 occurs at the endo-substituted P atom of 69+ and initiates a P–P bond cleavage in the respective P3-ring.

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