Generation of the First Persistent Phosphirenylium Cation

Laali, Kenneth K.; Geißler, Bernhard; Wagner, O.; Hoffmann, Jürgen; Armbrust, Ralph; Eisfeld, Wolfgang; Regitz, Manfred

doi:10.1021/ja00099a099

Cited by 54 publications

(34 citation statements)

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“…(78)]. [248] Cation 34 is a highly reactive species with a 31 P resonance in the 31 P NMR spectrum at 309.7 ppm. A close relative has been stabilized as a h 3 -nickel complex.…”

Section: H 4 P]mentioning

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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“…(78)]. [248] Cation 34 is a highly reactive species with a 31 P resonance in the 31 P NMR spectrum at 309.7 ppm. A close relative has been stabilized as a h 3 -nickel complex.…”

Section: H 4 P]mentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…Structures The π-aromaticity [5] and inherent chemical lability [6,8] of phosphirenylium cations have been discussed previously. The nitrogen rings are similar.…”

Section: π-Aromatic Compoundsmentioning

confidence: 99%

“…It is the lowest energy conformer on the C 2 H 2 P + energy surface [5]. It was first synthesized in 1994 [6] in liquid SO 2 and discussed [7] as an intermediate in the nucleophilic substitution of 2. Cation 1 is isoelectronic with the cyclopropenium cation and should therefore be aromatic, as calculations indicate [8].…”

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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“…In the same vein, a highly reactive dicoordinate phosphirenylium cation has been characterized in liquid SO 2 at low temperature [174].…”

Section: Three-membered Rings: Phosphiranes and Phosphirenesmentioning

confidence: 94%

Phosphorus Heterocycles

Mathey

2011

Modern Heterocyclic Chemistry

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Figure 23.1 The three isomers of the phosphole system (A-C) and the phospholide ion (D).2072j 23 Phosphorus Heterocycles shown with 1-alcoxyphospholes, which are relatively flat with a negligible delocalization [12]. Contrary to phospholes, the structure of phospholide ions reflects their high aromaticity. For example, the planar 2,3,4,5-tetramethylphospholide with Li(TMEDA) þ as the counterion displays the following parameters [13]: P-C, 1.715 A ; C¼C, 1.396 A ; CÀC, 1.424 A ;

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Generation of the First Persistent Phosphirenylium Cation

Cited by 54 publications

References 0 publications

Phospha‐Organic Chemistry: Panorama and Perspectives

Phospha‐Organic Chemistry: Panorama and Perspectives

σ*-Aromaticity in Three-Membered Rings

Phosphorus Heterocycles

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