6151-88-8

Upstream product

• 6224-63-1 tri(m-tolyl)phosphine 
• 73116-98-0 4,4,5,5-Tetramethyl-2,2,2-tri-m-tolyl-2λ⁵-[1,3,2]dioxaphospholane 
• 625-95-6 3-Iodotoluene 
• 791-28-6 Triphenylphosphine oxide 
• 591-17-3 meta-bromotoluene 
• 145290-34-2 bis(3-methylphenyl)phosphine oxide 

Downstream Products

• 123120-16-1 C₂₁H₁₈Br₃OP 
• 6224-63-1 tri(m-tolyl)phosphine 
• 1449430-77-6 (E)-[2-(1,2-diphenylethenyl)-5-methylphenyl]bis(3-methylphenyl)phosphine oxide 

Relevant academic research and scientific papers

Enhanced Luminescence of Asymmetrical Seven-Coordinate EuIII Complexes Including LMCT Perturbation

Luminescent mononuclear seven-coordinate EuIII complexes, with monocapped-octahedral (point group: C3v), monocapped-trigonal-prismatic (C2v), and pentagonal-bipyramidal (D5h) coordination structures, are reporte

A Mononuclear Non-Heme Manganese(III)-Aqua Complex in Oxygen Atom Transfer Reactions via Electron Transfer

Metal-oxygen complexes, such as metal-oxo [M(O2-)], -hydroxo [M(OH-)], -peroxo [M(O22-)], -hydroperoxo [M(OOH-)], and -superoxo [M(O2?-)] species, are capable of conducting oxygen atom transfer (OAT) reactions with organic substrates, such as thioanisole (PhSMe) and triphenylphosphine (Ph3P). However, OAT of metal-aqua complexes, [M(OH2)]n+, has yet to be reported. We report herein OAT of a mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), to PhSMe and Ph3P derivatives for the first time; it is noted that no OAT occurs from the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2), to the substrates. Mechanistic studies reveal that OAT reaction of 1 occurs via electron transfer from 4-methoxythioanisole to 1 to produce the 4-methoxythioanisole radical cation and [(dpaq)MnII(OH2)]+, followed by nucleophilic attack of H2O in [(dpaq)MnII(OH2)]+ to the 4-methoxythioanisole radical cation to produce an OH adduct radical, 2,4-(MeO)2C6H3S?(OH)Me, which disproportionates or undergoes electron transfer to 1 to yield methyl 4-methoxyphenyl sulfoxide. Formation of the thioanisole radical cation derivatives is detected by the stopped-flow transient absorption measurements in OAT from 1 to 2,4-dimethoxythioanisole and 3,4-dimethoxythioanisole, being compared with that in the photoinduced electron transfer oxidation of PhSMe derivatives, which are detected by laser-induced transient absorption measurements. Similarly, OAT from 1 to Ph3P occurs via electron transfer from Ph3P to 1, and the proton effect on the reaction rate has been discussed. The rate constants of electron transfer from electron donors, including PhSMe and Ph3P derivatives, to 1 are fitted well by the electron transfer driving force dependence of the rate constants predicted by the Marcus theory of outer-sphere electron transfer.

Microwave assisted P–C coupling reactions without directly added P-ligands

Our group introduced a green protocol for the Pd(OAc)2- or NiCl2-catalyzed P–C coupling reaction of aryl halides and various > P(O)H-compounds under MW conditions without directly added P-ligands. The reactivity of a few aryl derivatives in the Pd(OAc)2-catalyzed Hirao reaction was also studied. An induction period was observed in the reaction of bromobenzene and diphenylphosphine oxide. Finally, the less known copper(I)-promoted P–C coupling reactions were investigated experimentally. The mechanism was explored by quantum chemical calculations.

Air-stable phosphine organocatalysts for the hydroarsination reaction

Readily-available triarylphosphines are explored as organocatalysts for the hydroarsination reaction. When compared to transition metal catalysis, phosphine organocatalysis greatly improved solvent compatibility of the hydroarsination of nitrostyrenes. Upon complete conversion, arsine products were isolated in up to 99% yield while up to 48% of the phosphine catalyst was still active. A mechanism was proposed and structure-activity analysis regarding catalyst activity concluded that sterically-bulkier catalysts were effective at minimizing catalyst deactivation.

Molecular and crystal structures of tris(3-methylphenyl)phosphine and its chalcogenides

The molecular and crystal structures of tris(3-methylphenyl)phosphine, tris(3-methylphenyl)phosphine oxide, tris(3-methylphenyl)phosphine sulfide and tris(3-methylphenyl)phosphine selenide were determined by X-ray diffraction. It was previously indicated

Visible light-induced 4-phenylthioxanthone-catalyzed aerobic oxidation of triarylphosphines

We report herein a visible light-induced oxidation of triarylphosphines under aerobic condition with excellent functional group tolerance. In this transformation, the photo catalyst 4-phenylthioxanthone acted as a photosensitizer for the in situ generation of singlet oxygen. This new approach provided a cheaper and greener method for the preparation of phosphine oxide, showing great advantages in environmental protocols.

Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen

The metal-free reduction of phosphane oxides with molecular hydrogen (H2) using oxalyl chloride as activating agent was achieved. Quantum-mechanical investigations support the heterolytic splitting of H2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).

Eosin Y-catalyzed photooxidation of triarylphosphines under visible light irradiation and aerobic conditions

We report herein a novel method for Eosin Y-catalyzed photooxidation of triarylphosphines under visible light irradiation and aerobic conditions. This new approach employed visible light as the energy source and air as the oxidant, showing great advantages in environmental benignness and operational easiness with a wide functional group tolerance.

Direct oxygen atom transfer versus electron transfer mechanisms in the phosphine oxidation by nonheme Mn(IV)-oxo complexes

Direct oxygen atom transfer from a nonheme Mn(iv)-oxo complex, [(Bn-TPEN)MnIV(O)]2+, to triphenylphosphine (Ph3P) derivatives occurs with a significant steric effect resulting from the ortho-substituents on the phenyl group of the Ph3P derivatives, whereas the phosphine oxygenation by a Mn(iv)-oxo complex in the presence of HOTf occurs via an electron transfer mechanism without the substrate-steric effect.

Aryl group - A leaving group in arylphosphine oxides

The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when treated with organolithium reagent.