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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

Examples of polyphosphorus compounds obtained by the functionalization of P4 by nucleophiles (1), electrophiles (2), predominantly nucleophilic ambiphiles (3), and predominantly electrophilic ambiphiles (4).
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fig2: Examples of polyphosphorus compounds obtained by the functionalization of P4 by nucleophiles (1), electrophiles (2), predominantly nucleophilic ambiphiles (3), and predominantly electrophilic ambiphiles (4).

Mentions: One is the reaction of Mes*Li (Mes* = 2,4,6-tri-tert-butylphenyl) with one equivalent of P4 yielding a tetraphosphanide intermediate of type A. Subsequent reaction with Mes*Br yields the butterfly-type species 1 (Fig. 2).8 Further degradation of 1 is prevented by the sterically demanding Mes*-groups. Nucleophiles based on silicon, main group 5 or main group 6 elements were also employed.6 An electrophile may attack at a non-bonding orbital of lone pair character (HOMO – 6, –7.5 eV)7 which results in the formation of compounds of type B (Fig. 1II a). Alternatively, an electrophile may attack at a bonding orbital at one of the edges of the tetrahedron (HOMO, –6.7 eV; Fig. 1II b). However, this mode of attack is commonly less productive for main group element centered electrophiles and is not depicted. In total, only very few reactions with electrophiles were reported due to the low nucleophilicity of P4.9 One example constitutes the reaction of P4 with two equivalents of the sterically encumbered Lewis acid Ga(t-Bu)3. This yields compound 2; however, mechanistic details regarding its formation were not reported (Fig. 2).10


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

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

Examples of polyphosphorus compounds obtained by the functionalization of P4 by nucleophiles (1), electrophiles (2), predominantly nucleophilic ambiphiles (3), and predominantly electrophilic ambiphiles (4).
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig2: Examples of polyphosphorus compounds obtained by the functionalization of P4 by nucleophiles (1), electrophiles (2), predominantly nucleophilic ambiphiles (3), and predominantly electrophilic ambiphiles (4).
Mentions: One is the reaction of Mes*Li (Mes* = 2,4,6-tri-tert-butylphenyl) with one equivalent of P4 yielding a tetraphosphanide intermediate of type A. Subsequent reaction with Mes*Br yields the butterfly-type species 1 (Fig. 2).8 Further degradation of 1 is prevented by the sterically demanding Mes*-groups. Nucleophiles based on silicon, main group 5 or main group 6 elements were also employed.6 An electrophile may attack at a non-bonding orbital of lone pair character (HOMO – 6, –7.5 eV)7 which results in the formation of compounds of type B (Fig. 1II a). Alternatively, an electrophile may attack at a bonding orbital at one of the edges of the tetrahedron (HOMO, –6.7 eV; Fig. 1II b). However, this mode of attack is commonly less productive for main group element centered electrophiles and is not depicted. In total, only very few reactions with electrophiles were reported due to the low nucleophilicity of P4.9 One example constitutes the reaction of P4 with two equivalents of the sterically encumbered Lewis acid Ga(t-Bu)3. This yields compound 2; however, mechanistic details regarding its formation were not reported (Fig. 2).10

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