ChemInform Abstract: Diphosphetes—Substituent Stabilized Ring Systems.
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2001 structure structure (organic substances) K 9000 11 - 023 Diphosphetes–Substituent Stabilized Ring Systems. — The previously postulated stepwise mechanism of the formation of σ 2 P,σ 4 P-1,2- diphosphetes as (I) through reaction of phosphaacetylene with phosphinocarbene is confirmed by quantum chemical methods.Investigation of different calculated structural and electron density related parameters and the molecular orbitals reveals that electron delocalization plays an important role in the stabilization of (I) and, thus, affirms the crucial role of the amino (on σ 4 -P) and the silyl (on neighbouring C) substituent, which both together increase electron delocalization. Increasing the valence of the σ 2 -P atom through substitution, e.g. (II), destabilizes the diphosphete ring, which remains only stable as result of the effect of amino and silyl substituents. — (BERTRAND, GUY; EISFELD, WOLFGANG; NYULASZI, LASZLO; REAU, REGIS; REGITZ, MANFRED; SZIEBERTH, DENES; Perkin 2 (2000) 11, 2324-2327; Lab. Chim. Coord., CNRS, Inst. Natl. Polytech., Univ. Paul Sabatier, F-31077 Toulouse, Fr.; EN) 1
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Transcript of ChemInform Abstract: Diphosphetes—Substituent Stabilized Ring Systems.
2001 structure
structure (organic substances)K 9000
11 - 023Diphosphetes–Substituent Stabilized Ring Systems. — Thepreviously postulated stepwise mechanism of the formation of σ2P,σ4P-1,2-diphosphetes as (I) through reaction of phosphaacetylene with phosphinocarbeneis confirmed by quantum chemical methods.Investigation of different calculatedstructural and electron density related parameters and the molecular orbitalsreveals that electron delocalization plays an important role in the stabilizationof (I) and, thus, affirms the crucial role of the amino (on σ4-P) and thesilyl (on neighbouring C) substituent, which both together increase electrondelocalization. Increasing the valence of the σ2-P atom through substitution,e.g. (II), destabilizes the diphosphete ring, which remains only stable as result ofthe effect of amino and silyl substituents. — (BERTRAND, GUY; EISFELD,WOLFGANG; NYULASZI, LASZLO; REAU, REGIS; REGITZ, MANFRED;SZIEBERTH, DENES; Perkin 2 (2000) 11, 2324-2327; Lab. Chim. Coord.,CNRS, Inst. Natl. Polytech., Univ. Paul Sabatier, F-31077 Toulouse, Fr.; EN)
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