Highly Strained Organophosphorus Compounds

Slootweg, J. Chris

doi:10.1002/9781118299715.ch9

Cited by 8 publications

(5 citation statements)

References 185 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Extreme structural perturbations are potentially useful in developing ligands with unique properties . For example, the three-membered ring in the highly pyramidalized phosphiranes results in smaller cone angles and higher barriers to pyramidal inversion than in other phosphines . However, their coordination chemistry and use in catalysis have been little explored .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Metal Complexes of P-Stereogenic Chiral Phosphiranes: An EDA-NOCV Analysis of the Donor–Acceptor Properties of Phosphirane Ligands

et al. 2018

View full text Add to dashboard Cite

Reaction of the enantiomerically enriched P-stereogenic phosphiranes syn-(R P ,S C )-Mes*PCH 2 CH(Ph) (syn-1) and anti-(S P ,S C )-Mes*PCH 2 CH(Ph) (anti-2, Mes* = 2,4,6-(t-Bu) 3 C 6 H 2 ) with metal complex precursors gave Au(L)(Cl) (L = 1 (3); L = 2 (4)), trans-ML 2 Cl 2 (L = 1, M = Pd (5), Pt ( 6)), Pd(η 3 -C 3 H 5 )(L)(Cl) (L = 1 (7)), and trans-RhL 2 (CO)(Cl) (L = 1 (8); L = 2 (9)); 3, 4, 7, and 9 were crystallographically characterized. Phosphirane coordination resulted in shortening of the P−C bonds and increased bond angles at P, consistent with rehybridization at phosphorus. A comparison of complexes of phenylphosphirane and phenyldimethylphosphine using IR spectra, coupled with DFT studies using electronic decomposition analysis (EDA) and natural orbitals for chemical valence (NOCV), indicated that phosphiranes are slightly poorer σ-donors than the analogous phosphines and that the π-acceptor properties of these ligands are similar. Pauli repulsion, dispersion, and electrostatic attraction are also important factors in determining the strength of these metal−ligand interactions.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Metal Complexes of P-Stereogenic Chiral Phosphiranes: An EDA-NOCV Analysis of the Donor–Acceptor Properties of Phosphirane Ligands

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The 1 H and 13 C NMR chemical shifts for the AlC 2 H 4 moiety are observed at a high field: δ = −1.40 ppm and δ = 1.9 ppm, respectively. The ring Al−C and C−C bond lengths are 1.9669(18)/1.9510 (17), 1.9473(16)/ 1.9632 (18), and 1.587(2)/1.596(2) Å, respectively. Exposure of the benzene solution of AlC 2 -14 to a CO (1 bar) atmosphere at room temperature afforded dialuminum 10-1 as dark orange crystals in 23% yield.…”

Section: Al 1 E 2 Systemsmentioning

confidence: 99%

“…For instance, metal-catalyzed silylene transfer from silacyclopropanes to alkenes allows access to novel silacycles . A few phosphiranes and phosphirenes are used as ligands for transition-metal complexes relevant to catalysis and medicinal chemistry . Thiiranes show pharmacological activities, and they have been studied particularly for the development of anticancer and antiviral agents. , To date, a variety of group 14, 15, and 16 element rings have been documented …”

Section: Introductionmentioning

confidence: 99%

Three-Membered Aluminacycles

Yan

Kinjo

2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Three-membered-ring scaffolds of carbocycles, namely, cyclopropanes and cyclopropenes, are ubiquitous in natural products and pharmaceutical molecules. These molecules exhibit a peculiar reactivity, and their applications as synthetic intermediates and versatile building blocks in organic synthesis have been extensively studied over the past century. The incorporation of heteroatoms into three-membered cyclic structures has attracted significant attention, reflecting fundamental differences in their electronic/geometric structures and reactivities compared to their carbon congeners and their associated potential for exploitation in applications. Recently, the chemistry of low-valent aluminum species, alumylenes, dialumenes, and aluminyl anions, has dramatically developed, which has allowed access to hitherto unprecedented aluminacycles. This Perspective focuses upon advances in the chemistry of three-membered aluminacycles, including their synthetic protocols, spectroscopic and structural properties, and reactivity toward various substrates and small molecules.

show abstract

“…Given the ease with which 1 reacts with silylene 2 and Ph 3 PCH 2 , we investigated phosphiranation reactions of alkenes using 1 as the phosphinidene synthon. Note that phosphiranes are interesting targets given their applications as ligands for transition-metal catalysts, − polymer precursors, , and building blocks for organophosphorus compounds . Multiply bonded late transition-metal complexes are well-known tools for forging three-membered rings, such as cyclopropanes and aziridines. − Moreover, Hillhouse and co-workers demonstrated that phosphinidene transfer to ethylene may be achieved via a nickel phosphinidene complex; therefore, we employed nickel reagents in our initial investigation.…”

mentioning

confidence: 99%

Reactions of Tri-tert-Butylphosphatetrahedrane as a Spring-Loaded Phosphinidene Synthon Featuring Nickel-Catalyzed Transfer to Unactivated Alkenes

2022

View full text Add to dashboard Cite

Cage-opening reactions of the highly strained tri-tert-butylphosphatetrahedrane (1), shown here to function as a synthon of (tri-tert-butylcyclopropenyl)phosphinidene, are described. Treatment of 1 with a base-stabilized silylene led to the corresponding phosphasilene, which was isolated in 72% yield as a red crystalline solid. Phosphinidene transfer was also observed when 1 (2 equiv) was combined with the Wittig reagent Ph3PCH2 to form a diphosphirane (50% isolated yield). The reaction is proposed to proceed through a generated phosphaalkene intermediate, which was characterized by NMR spectroscopy. In addition, we report on nickel-catalyzed phosphinidene transfer to styrene, ethylene, neohexene, and 1,3-cyclohexadiene; the corresponding phosphiranes were isolated in 51–64% yield. Computational studies suggest the intermediacy of a nickel phosphinidene species. Treatment of the ethylene-derived phosphirane product with triflic acid delivered elimination of [ t Bu3C3]OTf and formation of a P–H bond, illustrating the ability of the tri-tert-butyl cyclopropenyl group to serve as a protecting group that is removable following phosphinidene transfer.

show abstract

Highly Strained Organophosphorus Compounds

Cited by 8 publications

References 185 publications

Synthesis and Structure of Metal Complexes of P-Stereogenic Chiral Phosphiranes: An EDA-NOCV Analysis of the Donor–Acceptor Properties of Phosphirane Ligands

Synthesis and Structure of Metal Complexes of P-Stereogenic Chiral Phosphiranes: An EDA-NOCV Analysis of the Donor–Acceptor Properties of Phosphirane Ligands

Three-Membered Aluminacycles

Reactions of Tri-tert-Butylphosphatetrahedrane as a Spring-Loaded Phosphinidene Synthon Featuring Nickel-Catalyzed Transfer to Unactivated Alkenes

Contact Info

Product

Resources

About