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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.


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Carbene-induced transformation and fragmentation reactions of P4.
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sch18: Carbene-induced transformation and fragmentation reactions of P4.

Mentions: The activation of white phosphorus with carbenes, which belong to the class of predominantly nucleophilic ambiphiles, displays one of the most diverse fields of P4 chemistry.6 The cyclo-triphosphirene derivative C constitutes a key intermediate in all transformations, independent of the characteristic of the respective carbene employed (Fig. 1). However, intermediate C is elusive and distinct reaction pathways occur depending on the electronic and steric features of carbene L (Scheme 18). Bertrand and co-workers reacted P4 with carbenes L1 and L3 in a 1 : 2 stoichiometry and obtained E/Z isomers 64a,bvia an intermediate of type C.12 Bicyclic species 65 is the result of a cyclo-addition reaction involving the phosphorus double bond of an intermediate of type C and the alkyl amino carbene L4.66 Compound 66 results from a ring-opening reaction of an intermediate C with two equivalents of L5.66 This reaction is accompanied by the formation of 67 as a side product. This P2-species is formed by the formal [2+2] fragmentation of P4 by carbene L5. A [3+1]-fragmentation of the P4 tetrahedron was achieved using the sterically less demanding carbene L6 in a reaction with P4 in a 3 : 1 stoichiometry.66 The P1-fragment was identified as 68+ and isolated as chloride salt. The presence of chloride anions is explained by the decomposition of CHCl3 solvent molecules.


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

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

Carbene-induced transformation and fragmentation reactions of P4.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

sch18: Carbene-induced transformation and fragmentation reactions of P4.
Mentions: The activation of white phosphorus with carbenes, which belong to the class of predominantly nucleophilic ambiphiles, displays one of the most diverse fields of P4 chemistry.6 The cyclo-triphosphirene derivative C constitutes a key intermediate in all transformations, independent of the characteristic of the respective carbene employed (Fig. 1). However, intermediate C is elusive and distinct reaction pathways occur depending on the electronic and steric features of carbene L (Scheme 18). Bertrand and co-workers reacted P4 with carbenes L1 and L3 in a 1 : 2 stoichiometry and obtained E/Z isomers 64a,bvia an intermediate of type C.12 Bicyclic species 65 is the result of a cyclo-addition reaction involving the phosphorus double bond of an intermediate of type C and the alkyl amino carbene L4.66 Compound 66 results from a ring-opening reaction of an intermediate C with two equivalents of L5.66 This reaction is accompanied by the formation of 67 as a side product. This P2-species is formed by the formal [2+2] fragmentation of P4 by carbene L5. A [3+1]-fragmentation of the P4 tetrahedron was achieved using the sterically less demanding carbene L6 in a reaction with P4 in a 3 : 1 stoichiometry.66 The P1-fragment was identified as 68+ and isolated as chloride salt. The presence of chloride anions is explained by the decomposition of CHCl3 solvent molecules.

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