1-Methyl-1-phenylphosphiranium triflate: synthesis, structure and reactivity

Hockless, David C. R.; McDonald, Mark A.; Pabel, Michael; Wild, S. Bruce

doi:10.1039/c39950000257

Cited by 43 publications

(31 citation statements)

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“…They form colorless crystals which melt without decomposition and can be handled in air. In contrast to 1-phenylphosphirane, PhP(CH 2 ) 2 , 5 a and 5 b do not react even with an excess of strong alkylating agents such as MeOSO 2 CF 3 to form phosphiranium salts, [9] nor do they react with sulfur in refluxing toluene to give thiophosphoranes.…”

Section: Dedicated To Professor Edgar Niecke On Occasion Of His 60th mentioning

confidence: 99%

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Very Stable Phosphiranes

Liedtke

Loss

Alcaraz

et al. 1999

Angew. Chem. Int. Ed.

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Section: Dedicated To Professor Edgar Niecke On Occasion Of His 60th mentioning

confidence: 99%

“…[9] Since fluorescence is a very sensitive technique measurements of the self-diffusion coefficient can be extended to very low concentrations.…”

mentioning

confidence: 99%

Very Stable Phosphiranes

Liedtke

Loss

Alcaraz

et al. 1999

Angew. Chem. Int. Ed.

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“…Finally, the dissociation of phosphirane derivatives into alkenes and low-coordinate phosphorus units is well documented for terrvalent phosphiranes, [134] phosphirane oxides, [187] phosphiranium salts, [188] and phosphirane complexes. [189] It has also been studied from a theoretical standpoint.…”

Section: Bent Bonds and Strained Ringsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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“…Hockless et al [10] synthesized the 1H-phosphirenium cations 3 by exchange of the saturated C 2 -moiety in phosphiranium cations 4 by an unsaturated one, which is an indication of an excess σ*-aromatic stabilization in unsaturated rings. This effect has been demonstrated by comparing the dihydrogen-rings with their halogen disubstituted coun-P Y Scheme 2 Fluoro-disubstituted cyclopropene is stabilized and cyclopentadiene destabilized by hyperconjugation relative to the hydrogen-disubstituted rings; energies in kJ mol -1 [13] Figure 1 Stabilizing interaction of the double bond π-MO with the σ*-MO formed by the p z orbital at atom X and the p x -orbitals at ligands Y (X = P, Si, N, C; Y = F, Cl, Br, H) π σ σ * terparts.…”

Section: Introductionmentioning

confidence: 99%

σ*-Aromaticity in Three-Membered Rings

Göller

Clark

2000

J Mol Model

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The structures and energies of unsaturated three-membered rings of the general formula (CH) 2 XY n m , with charge = m and n substituents Y at X (Y = fluorine, chlorine, bromine, hydrogen, X = phosphorus, silicon, nitrogen, carbon) are compared to their saturated analogs. The structures were optimized with B3LYP/6-311+G(2d,p) and at MP2/6-31+G(d), with single point energy calculations on the latter geometries at MP4SDTQ/6-31+G(d). The geometrical changes in bond lengths and angles, which correlate with substituent electronegativities, are discussed for the different ring systems. The relative stabilities of unsaturated and saturated rings are compared using isodesmic ring-opening reactions and homodesmic substituent-exchange reactions. σ*-Aromaticity, a hyperconjugative effect found in the disubstituted rings, causes lowering of ring strain energies for the unsaturated rings and preference of unsaturated rings over saturated ones for the more electronegative substituents. For the mono-substituted π-aromatic silacyclopropenes and cyclopropenes, a destabilization by more electronegative ligands is found. For the neutral rings monosubstituted at main group V atoms like the 1H-phosphirenes and also the isoelectronic negatively charged rings with main group IV atoms like the silacyclopropenium anions, no correlation of stabilization energies or geometrical changes with ligand electronegativity is found.

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1-Methyl-1-phenylphosphiranium triflate: synthesis, structure and reactivity

Abstract: A us t ra lia 1 -P h enyl p hosp h i ra ne reacts with methyl trif late to give 1 -methyl-1 -p hen yl p hosp h i ra n i u m t riflate, which reacts with acetylenes to give the corresponding phosphirenium salts.

Cited by 43 publications

References 11 publications

Very Stable Phosphiranes

Very Stable Phosphiranes

Phospha‐Organic Chemistry: Panorama and Perspectives

σ*-Aromaticity in Three-Membered Rings

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