The σ‐donating and π‐accepting properties of ortho‐Si(CH3)3 phosphinine macrocycles

Ferro, Víctor R.; Omar, Salama; González-Jonte, R. H.; Vega, José Manuel García de la

doi:10.1002/hc.10118

Cited by 10 publications

(21 citation statements)

References 25 publications

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“…Two phosphorous atoms point towards the top of the cavity and are located above the plane defined by the three silicon atoms whereas the third one points below the plane. 1,2 Semiempirical PM3 calculations, 3 on the whole, reproduce the geometry experimentally observed for these compounds. Nevertheless, they failed when reproducing the strong nonplanarity of the silacalix [3]phosphinine: its PM3 optimized geometry is more planar than that obtained experimentally.…”

Section: Introductionmentioning

confidence: 55%

“…Their synthesis and X-ray crystal characterization were first developed by Avarvari et al, 1,2 who obtained the three-and four-silacalixphosphinines, as well as the mixed thiophene-and furan-derivatives of the latter. X-ray studies 1,2 have revealed that these compounds are strongly deviated with respect to the plane, the silacalix [3]phosphinine being much more distorted than the silacalix [4]phosphinine.…”

Section: Introductionmentioning

confidence: 98%

“…However, this is not so as we have seen in semiempirical calculations. 3 This suggests the complexity of the electron structure of this class of compounds along with the difficulties in its description.…”

Section: Introductionmentioning

confidence: 99%

“…1,2 The silacalix [3]phosphinine adopts a partial cone-type structure. Two phosphorous atoms point towards the top of the cavity and are located above the plane defined by the three silicon atoms whereas the third one points below the plane.…”

Section: Introductionmentioning

confidence: 99%

“…

Abstract: A broad set of structural models and theoretical methods has been successfully used for studying both the molecular electron structure of the silacalix [3]phosphinine and the changes of the macrocycle core under the conditions that frequently correspond to its complexes with metals. The macrocycle core of the silacalix[3]phosphinine and its neutral derivatives are strongly deviated from the main molecular plane.

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confidence: 99%

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On the molecular electron structure of three phosphinine‐containing macrocycles

2007

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A broad set of structural models and theoretical methods has been successfully used for studying both the molecular electron structure of the silacalix[3]phosphinine and the changes of the macrocycle core under the conditions that frequently correspond to its complexes with metals. The macrocycle core of the silacalix[3]phosphinine and its neutral derivatives are strongly deviated from the main molecular plane. The phosphorous electron lone pairs and the pi-cloud of the phosphinine units give the main contribution to the electron valence structure in the silacalix[3]phosphinine and also in its both oxidized and reduced derivatives. Although the electron lone pairs of the P atoms tend to be strongly repulsive, they are either totally or partially extended above all the fragment of the phosphorous atoms depending on geometrical factors or even strongly coupled with the pi-cloud of the phosphinine units. Electronic processes that take away part of the electron density from the macrocyle favor both its planar configuration and the asymmetric distribution of the valence electrons in the silacalix[3]phosphinine and its derivatives. The limit condition to this effect is the appearance of a new in-plane sigma molecular orbital between the P atoms of two neighboring phosphinine units.

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Section: Introductionmentioning

confidence: 55%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the molecular electron structure of three phosphinine‐containing macrocycles

2007

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2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Habicht

Wossidlo

Bens

et al. 2017

Chemistry A European J

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The [4+2] cycloaddition reaction between 2-pyrone and Me Si-C≡P gives the corresponding 2-(trimethylsilyl)-λ -phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium-labeling experiments. The silyl-phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine-Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C H P by means of protodesilylation with HCl. C H P reacts with CuBr⋅S(CH ) to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the -Si(CH ) group on the electronic properties of the aromatic phosphorus heterocycle.

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Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

Wossidlo

Frost

Lin

et al. 2021

Chemistry A European J

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The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of 1 J P,Se = 883 Hz is in line with a PÀ Se bond of high s-character. The σ-electron donating Me 3 Sisubstituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C 5 H 5 P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I) Cl as well as i PrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.

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The σ‐donating and π‐accepting properties of ortho‐Si(CH₃)₃ phosphinine macrocycles

Cited by 10 publications

References 25 publications

On the molecular electron structure of three phosphinine‐containing macrocycles

On the molecular electron structure of three phosphinine‐containing macrocycles

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

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The σ‐donating and π‐accepting properties of ortho‐Si(CH3)3 phosphinine macrocycles

Cited by 10 publications

References 25 publications

On the molecular electron structure of three phosphinine‐containing macrocycles

On the molecular electron structure of three phosphinine‐containing macrocycles

2‐(Trimethylsilyl)‐λ3‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

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Product

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The σ‐donating and π‐accepting properties of ortho‐Si(CH₃)₃ phosphinine macrocycles

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity