Phosphaalkynes – Starting Point for the Synthesis of Phosphorus‐Carbon Cage Compounds

Regitz, Manfred; Hoffmann, A.; Bergsträbter, U.

doi:10.1002/9783527615278.ch06

Cited by 16 publications

(4 citation statements)

References 82 publications

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“…Due to their unsaturation and high, novel reactivity, phosphaalkynes (or phosphaacetylenes) play a very important role in low-coordinate phosphaorganic chemistry . The parent compound phosphaethyne (HCP) was synthesized first in 1961 .…”

Section: Introductionmentioning

confidence: 99%

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Formation of Phosphaalkyne Trimers: A Mechanistic Study

Höltzl¹,

Nguyen²,

Veszprémi

2010

Organometallics

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The geometric and electronic structures of phosphaethyne trimers were studied using density functional theory (B3LYP/cc-pVTZ) as well as CBS-QB3, CCSD(T), and complete active space selfconsistent field (CASSCF) computations. The effect of the substituents was also investigated. Our aim was to identify the low-energy equilibrium structures with synthetic interest; therefore, we were determining minima without any restriction on the chemical structure. The global minimum of the C 3 P 3 H 3 potential energy surface is confirmed to be the 1,2,3-triphosphinine. The next energetically stable isomer is a potentially synthesizable target with a P 3 ring, which is only 34 kJ/mol above the global minimum. Formation of phosphaethyne trimers by reaction of phosphaethyne and 1,4diphosphatriafulvene has been determined. This suggests that the thermodynamically controlled product is the 1,3,5-triphosphinine, while 1,3,6-triphosphafulvene is the kinetically favored product. For the latter a biradical reaction pathway also exists. Analysis of the effect of the substituents shows that the reaction barriers increase with the size of the substituent. Using the bulky 2,4,6-tri-tertbutylphenyl (supermesityl) substituent, the relative stabilities of 1,3,5-triphosphinine and 1,3,6triphosphafulvene are reversed, and the latter is expected to be the most stable phosphaalkyne trimer with bulky substituents. The head-to-tail reaction of phosphaethyne and phosphanylidene carbenoid yields 1,3,6-triphosphafulvene with very small barriers, while 1,4-diphosphafulvene is expected to be a byproduct. The results are in good agreement with the experimental findings.

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Section: Introductionmentioning

confidence: 99%

“…One of the most interesting reactions of phosphaalkynes is their oligomerization and polymerization . Polymerization of phosphaethyne yields a black compound.…”

Section: Introductionmentioning

confidence: 99%

Formation of Phosphaalkyne Trimers: A Mechanistic Study

Höltzl¹,

Nguyen²,

Veszprémi

2010

Organometallics

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“…The smaller steric bulk of the phenyl group also provides the reactive C'P bond in the monomer (and the CAP bond in its oligomers) with sufficient room for a greater number of oligomeric products with different regio-and stereochemistries to be formed relative to t-BuC'P. A presence of head-tohead cycloadducts may explain the thermal instability of the oligomers towards fragmentation with loss of P 4 . Future efforts will focus on the mechanism of degradation in the oligophosphaethynes and the oligomerization chemistry of phosphaethynes with even less sterically bulky substituents to determine if higher molecular weight polymers can be obtained.…”

Section: Resultsmentioning

confidence: 96%

Spontaneous polymerization of phenylphosphaethyne

Loy

Jamison

McClain

et al. 1999

J. Polym. Sci. A Polym. Chem.

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“…These compounds are readily converted to the corresponding phosphaalkynes, RCP, in a solvent using a Lewis base (DBU) or in the gas phase by reaction with a solid base (K 2 CO 3 ) . Phosphaalkyne synthons produced in this or in alternative manners have been used extensively in the last 25 years and have led to a rapid development of phosphorus chemistry. − …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of the Novel Compound Cyclopropylethylidynephosphine (C₃H₅CH₂C≡P)

2014

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The synthesis of the novel compound cyclopropylethylidynephosphine (C3H5CH2C≡P) and its microwave spectrum are reported together with quantum chemical calculations. The spectrum, which reveals the existence of two conformers, has been recorded in the 38-109 GHz spectral range at room temperature. The H-C-CH2-C chain of atoms is synclinal in one rotamer denoted sc, and antiperiplanar in the second conformer called ap. The spectra of the ground vibrational state and two vibrationally excited states were assigned for each rotamer. The vibrational frequencies of these excited states were determined by relative intensity measurements. Relative intensity measurements were also conducted to determine the energy difference between ap and sc. The latter conformer was found to be the lower-energy form and E(ap) - E(sc) was determined to be 0.9(4) kJ/mol. The microwave study has been augmented by quantum chemical calculations at the CCSD/cc-pVQZ and MP2/cc-pVTZ levels of theory. The CCSD predictions were generally in good agreement with experiment, while somewhat mixed results were obtained in the MP2 calculations.

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Phosphaalkynes – Starting Point for the Synthesis of Phosphorus‐Carbon Cage Compounds

Cited by 16 publications

References 82 publications

Formation of Phosphaalkyne Trimers: A Mechanistic Study

Formation of Phosphaalkyne Trimers: A Mechanistic Study

Spontaneous polymerization of phenylphosphaethyne

Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of the Novel Compound Cyclopropylethylidynephosphine (C₃H₅CH₂C≡P)

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Phosphaalkynes – Starting Point for the Synthesis of Phosphorus‐Carbon Cage Compounds

Cited by 16 publications

References 82 publications

Formation of Phosphaalkyne Trimers: A Mechanistic Study

Formation of Phosphaalkyne Trimers: A Mechanistic Study

Spontaneous polymerization of phenylphosphaethyne

Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of the Novel Compound Cyclopropylethylidynephosphine (C3H5CH2C≡P)

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Product

Resources

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Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of the Novel Compound Cyclopropylethylidynephosphine (C₃H₅CH₂C≡P)