Immobilized di(hydroperoxy)propane adducts of phosphine oxides as traceless and recyclable oxidizing agents

Hoefler, John C.; Vu, Anh; Perez, Arturo J.; Blümel, Janet

doi:10.1016/j.apsusc.2023.157333

Cited by 6 publications

(3 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, the Pake pattern of deuterium nuclei has been used widely for probing mobile species and moieties in the solid state. 13,22,41,42 Therefore, we synthesized three deuterated versions of 1 , PPh 3 - d 1 (Ph 2 P( p -C 6 H 4 D), 1- d 1 ), PPh 3 - d 3 (P( p -C 6 H 4 D) 3 , 1- d 3 ), and PPh 3 - d 5 (Ph 2 P(C 6 D 5 ), 1- d 5 ).…”

Section: Resultsmentioning

confidence: 99%

Adsorption of solid phosphines on silica and implications for catalysts on oxide surfaces

Hoefler,

Yang,

Blümel

2023

New J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

Adsorption of solid phosphines on silica and implications for catalysts on oxide surfaces

Hoefler,

Yang,

Blümel

2023

New J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The presented research shows that clean phosphine oxides can be obtained by surface-assisted oxidation in the atmosphere, without the need for expensive and potentially hazardous oxidizing agents like H 2 O 2 36 or di(hydroperoxy)alkanes. 39 − 45 The oxidation is therefore more benign, and the workup is much simpler than described previously 36 because no H 2 O 2 adducts of the phosphine oxides need to be destroyed. 36 In future projects, we will explore the potential of the surface-assisted oxidation with AC for other relevant oxidation reactions such as aldehyde oxidation 45 and epoxidations.…”

Section: Discussionmentioning

confidence: 99%

“…Importantly, as electron pair donors, phosphine oxides can form hydrogen bonds with a variety of species containing OH groups. − For example, phosphine oxides can create networks with phenols, and they engage in hydrogen bonding with water − and silanols . Phosphine oxides also have the ability to stabilize hydrogen peroxide and di(hydroperoxy)alkanes in the form of Hilliard adducts, , (R 3 PO·H 2 O 2 ) 2 , and Ahn adducts, − R 3 PO·(HOO) 2 CR’R″ (R,R′,R″ = alkyl, aryl). Finally, phosphine oxides interact strongly with various oxide surfaces like silica and alumina via hydrogen bonding. − …”

Section: Introductionmentioning

confidence: 99%

Surface-Assisted Selective Air Oxidation of Phosphines Adsorbed on Activated Carbon

Hoefler,

Jackson,

Blümel

2024

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

Trialkyl- and triarylphosphines readily adsorb onto the surface of porous activated carbon (AC) even in the absence of solvents through van der Waals interactions between the lone electron pair and the AC surface. This process has been proven by solid-state NMR techniques. Subsequently, it is demonstrated that the AC enables the fast and selective oxidation of adsorbed phosphines to phosphine oxides at ambient temperature in air. In solution, trialkylphosphines are oxidized to a variety of P(V) species when exposed to the atmosphere, while neat or dissolved triarylphosphines cannot be oxidized with air. When the trialkyl- and triarylphosphines P n Bu3 (1), PEt3, (2), P n Oct3 (3), PMe t Bu2 (4), PCy3 (5), and PPh3 (6) are adsorbed in a mono- or submonolayer on the surface of AC, in the absence of a solvent and at ambient temperature, they are quantitatively oxidized to the adsorbed phosphine oxides, 1 ox –6 ox , once air is admitted. No formation of any unwanted P(V) side products or water adducts is observed. The phosphine oxides can then be recovered in good yields by washing them off of the AC. The oxidation is likely facilitated by a radical activation of molecular oxygen due to delocalized electrons on the aromatic surface coating of AC, as proven by ESR. This easy and inexpensive oxidation method renders hydrogen peroxide or other oxidizers unnecessary and is broadly applicable to sterically hindered and even to air-stable triarylphosphines. Phosphines adsorbed at lower surface coverages on AC oxidize at a faster rate. All oxidation reactions were monitored by solution- and solid-state NMR spectroscopy.

show abstract

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

Vijai Anand,

Perinbanathan,

Singh

et al. 2024

ChemCatChem

View full text Add to dashboard Cite

Phosphine oxides are an interesting class of compounds possessing tetracoordinate and pentavalent phosphorus atoms and have been employed in a wide range of applications including reagents in organic synthesis, metal extractants, flame retardants, pharmaceuticals, and bioactivity studies. Among all, the degree of basicity of phosphoryl oxygen driven by the nature of substituents influences the electronic properties of the central metal in a complex toward the diversified catalytic processes. Further, the presence of heteroatoms adjacent to the central phosphorus atom enhances the nucleophilicity of the phosphoryl oxygen atom. In view of this, the present review covers the past two decades of remarkable catalytic versatility of P=O‐based metal complexes and describes the governing factors influencing the structural properties and the resultant coordination behavior. Interestingly, some of the P=O bond distances of metal complexes are either longer or shorter compared to their free ligands, indicating the catalytic activity. These complexes can effectively catalyze a wide range of chemical reactions including polymerizations, C‐C and Si‐C bond activations, oxidation, reduction, hydroformylation, hydrophosphination, hydrogenation and cyclization reactions. Furthermore, this review emphasizes the impact of substituents, solvents, additives, light, and temperature on the catalytic efficiency.

show abstract

Immobilized di(hydroperoxy)propane adducts of phosphine oxides as traceless and recyclable oxidizing agents

Cited by 6 publications

References 62 publications

Adsorption of solid phosphines on silica and implications for catalysts on oxide surfaces

Adsorption of solid phosphines on silica and implications for catalysts on oxide surfaces

Surface-Assisted Selective Air Oxidation of Phosphines Adsorbed on Activated Carbon

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

Contact Info

Product

Resources

About