- Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts
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Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.
- Gschwind, Ruth M.,Mende, Michael,Scott, Daniel J.,Streitferdt, Verena,Till, Marion,Wolf, Robert
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supporting information
p. 1100 - 1103
(2022/02/03)
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- Taylor, Nicholas P.,Gonzalez, Jorge A.,Nichol, Gary S.,García-Domínguez, Andrés,Leach, Andrew G.,Lloyd-Jones, Guy C.
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supporting information
p. 721 - 729
(2022/01/04)
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- Synthesis method of phosphine (III) compound
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The invention aims to provide an aryl phosphine oxide compound as a raw material, wherein P=O keys are activated by an acid anhydride and alkali is continued. The preparation of the phosphine (III) compound is carried out under the action of a crown ether and a reducing agent. The method has the advantages of cheap and easily available raw materials, simple operation, high atomic economy and the like. Compared with a traditional reduction mode, the method is ingenious in design, waste emission is reduced, separation of intermediate products is omitted, and related reagents such as silicon hydrogen, aluminum, boron and the like with higher price can be avoided. And the reaction suitability is extensive.
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Paragraph 0020
(2021/11/27)
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- Organic long afterglow material with photoactivation characteristic as well as preparation method and application thereof
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The invention discloses an organic long afterglow material with photoactivation characteristic, and a preparation method and application thereof. The chemical structure of the material has a general formula; and R in the formula is H, F, OCH3. According to the invention, the series of compounds are prepared by taking a triphenylphosphine oxide derivative as a research object and connecting different substituents to three benzene ring para-positions of triphenylphosphine oxide. after controlling of the ultraviolet irradiation time, the phosphorescence service life and the intensity of the series of materials are obviously improved. And in combination with different dynamic adjustability, multiple information encryption applications are realized.
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Paragraph 0050-0055
(2020/09/09)
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- Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
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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 %).
- Stepen, Arne J.,Bursch, Markus,Grimme, Stefan,Stephan, Douglas W.,Paradies, Jan
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supporting information
p. 15253 - 15256
(2018/10/24)
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- Ir(III)-catalyzed direct C-H functionalization of arylphosphine oxides: A strategy for MOP-type ligands synthesis
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Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C-H functionalization of arylphos-phine oxides. Involving C-H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework.
- Liu, Zhong,Wu, Ji-Qiang,Yang, Shang-Dong
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supporting information
p. 5434 - 5437
(2017/11/06)
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- Mild Reduction of Phosphine Oxides with Phosphites To Access Phosphines
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A new method for the iodine-catalyzed reduction of phosphine oxides with phosphites at room temperature is reported. The mild reaction conditions, scalability, and simple purification requirements render it a method of choice for the large-scale production and facile regeneration of a variety of phosphines. Mechanistic studies, supported by DFT calculations of the oxygen transfer between the starting phosphine oxide and the phosphite reagent, are also presented. Such transmutations of phosphorus species were previously unknown.
- Li, Peng,Wischert, Raphael,Métivier, Pascal
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supporting information
p. 15989 - 15992
(2017/11/01)
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- CATALYST SYSTEMS FOR PREPARING 1-HEXENE AND/OR 1-OCTENE FROM ETHYLENE
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This invention relates to a catalyst system for selective oligomerization of ethylene, which includes (i) a chromium compound; (ii) a ligand having a P—C—C—P backbone structure; and (iii) an activator, thus preparing 1-hexene and/or 1-octene with high activity and selectivity.
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Page/Page column
(2015/02/25)
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- Dual [Fe+Phosphine] catalysis: Application in catalytic wittig olefination
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Iron hydride complexes of the general formula P2Fe(NO)CO)H are highly active catalysts for the hydrosilylation of aldehydes or ketones and phosphine oxides. Depending on the solvent, the in situ reduction of the phosphine oxide can be faster than the corresponding hydrosilylation of a carbonyl group. This unusual activity was used within the context of catalytic Wittig olefination. Picture perfect: Iron hydride complexes of the general formula P2Fe(NO)CO)H are highly active catalysts for the hydrosilylation of aldehydes or ketones and phosphine oxides. Depending on the solvent, the in situ reduction of the phosphine oxide can be faster than the corresponding hydrosilylation of a carbonyl group. This unusual activity is used within the context of catalytic Wittig olefination. EWG=Electron-withdrawing group.
- Rommel, Susanne,Belger, Christian,Begouin, Jeanne-Marie,Plietker, Bernd
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p. 1292 - 1301
(2015/04/27)
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- The basicity of phosphines
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The basicities of the triarylphosphines P(4-XC6H4)3 (X = Cl, F, H, CH3, CH3O, (CH3)2N), P(3-CH3C6H4)3, and P(2-CH3C6H7)3 as well as the trialkylphosphines P(t-Bu)3 and PCy3 have been measured by the nitromethane titration method.The range of basicity available by aryl substitution is very large, being pKa = 8. 65 for X = (CH3)2N to 1.03 for X = Cl.The most basic phosphine is P(t-Bu)3 whose pKa = 11.40.The measured basicities correlate well wit ?p, ?Φ, and ν as well as with the lone pair ionisation potentials of the triarylphosphines.Generally the 1H,31P, and 13C nmr spectral parameters of the free and protonated phosphines do not correlate well with pKa.
- Allman, Tim,Goel, Ram G.
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p. 716 - 722
(2007/10/02)
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