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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

Generalized reactions of P4 with nucleophiles (I, Nu–), electrophiles (II, El+), predominantly nucleophilic ambiphiles (III, Ab), and predominantly electrophilic ambiphiles (IV, Ab); A–D illustrate structural motifs obtained after reaction with the aforementioned species.
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fig1: Generalized reactions of P4 with nucleophiles (I, Nu–), electrophiles (II, El+), predominantly nucleophilic ambiphiles (III, Ab), and predominantly electrophilic ambiphiles (IV, Ab); A–D illustrate structural motifs obtained after reaction with the aforementioned species.

Mentions: In order to gain an in depth understanding of the reactions of P4 and main group element compounds, it is crucial to understand the properties of the P4 tetrahedron. The bonding in P4 is almost “cluster-like”, strongly delocalized and mostly effected through 3p atomic orbitals. Interestingly, P4 shows spherical aromaticity and is virtually unstrained despite acute bond angles of 60°.7 Generalized reactions of P4 with nucleophiles (Nu–), electrophiles (El+) and ambiphiles (Ab) are shown in Fig. 1. Radical reactions involving P4 are excluded. A nucleophile (Nu–) interacts with the LUMO of P4 (–1.8 eV),7 which leads to the rupture of a P–P bond giving butterfly-type bicyclo[1.1.0]tetraphosphane A (Fig. 1I). The reactions of P4 with nucleophiles were intensely investigated using an array of organo-alkali and organo-alkali earth reagents.6 However, in many cases the formation of a derivative of A only constitutes the first step of a reaction sequence which ultimately leads to the degradation of P4 to P1-compounds.6 Only a few reactions involving a selective cleavage of only a single bond in the P4 tetrahedron are reported.


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

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

Generalized reactions of P4 with nucleophiles (I, Nu–), electrophiles (II, El+), predominantly nucleophilic ambiphiles (III, Ab), and predominantly electrophilic ambiphiles (IV, Ab); A–D illustrate structural motifs obtained after reaction with the aforementioned species.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig1: Generalized reactions of P4 with nucleophiles (I, Nu–), electrophiles (II, El+), predominantly nucleophilic ambiphiles (III, Ab), and predominantly electrophilic ambiphiles (IV, Ab); A–D illustrate structural motifs obtained after reaction with the aforementioned species.
Mentions: In order to gain an in depth understanding of the reactions of P4 and main group element compounds, it is crucial to understand the properties of the P4 tetrahedron. The bonding in P4 is almost “cluster-like”, strongly delocalized and mostly effected through 3p atomic orbitals. Interestingly, P4 shows spherical aromaticity and is virtually unstrained despite acute bond angles of 60°.7 Generalized reactions of P4 with nucleophiles (Nu–), electrophiles (El+) and ambiphiles (Ab) are shown in Fig. 1. Radical reactions involving P4 are excluded. A nucleophile (Nu–) interacts with the LUMO of P4 (–1.8 eV),7 which leads to the rupture of a P–P bond giving butterfly-type bicyclo[1.1.0]tetraphosphane A (Fig. 1I). The reactions of P4 with nucleophiles were intensely investigated using an array of organo-alkali and organo-alkali earth reagents.6 However, in many cases the formation of a derivative of A only constitutes the first step of a reaction sequence which ultimately leads to the degradation of P4 to P1-compounds.6 Only a few reactions involving a selective cleavage of only a single bond in the P4 tetrahedron are reported.

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