- Reactivity of [Pt(PtBu3)2] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn-Zn Bond Cleavage, and Cooperative Reactivity
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Metal-only Lewis pairs (MOLPs) based on zinc electrophiles are particularly interesting due to their relevance to Negishi cross-coupling reactions. Zinc-based ligands in bimetallic complexes also render unique reactivity to the transition metals at which
- Hidalgo, Nereida,Romero-Pérez, Carlos,Maya, Celia,Fernández, Israel,Campos, Jesús
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Read Online
- Raney-Ni reduction of phosphine sulfides
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A variety of tertiary phosphine sulfides have been reduced by Raney-Ni to give the corresponding phosphineswith high efficiency and undermild conditions. Alkyl, aryl, acyclic, cyclic, aswell as sterically crowded phosphine sulfides are reduced with equal facility. Optically active P-stereogenic phosphine sulfides are reduced stereospecifically with clean retention of configuration at P. Reductions of unsaturated phosphinesulfides is not fully chemoselective and takes place with concomitant partial reduction of the double bond. Clean reduction of the unsaturated phosphine sulfides to the corresponding fully saturated phosphines can be achieved in one step by running the reduction under H2atmosphere (balloon).
- Demchuk, Oleg M.,?wierczyńska, Wioletta,Dziuba, Kamil,Frynas, S?awomir,Flis, Anna,Pietrusiewicz, K. Micha?
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- Oxidative ring expansion of a low-coordinate palladacycle: Synthesis of a robust T-shaped alkylpalladium(II) complex
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The synthesis of an unusual T-shaped alkylpalladium(II) complex featuring a cyclometalated tri-tert-butylphosphineoxide ligand by oxidation of the corresponding cyclometalated tri-tert-butylphosphine complex with PhIO is reported. We speculate that this reaction proceeds by formation of a transient palladium oxo intermediate and there are structural similarities with a late transition metal exemplar: Milstein's seminal pincer ligated Pt(IV) oxo (Nature 2008, 455, 1093–1096).
- Sinclair, Matthew J.G.,Chaplin, Adrian B.
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Read Online
- 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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- Process for synthesizing tri-tert-butylphosphonium tetrafluoroborate
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A tert-butyl Grignard reagent is reacted with phosphorus trihalide and boron trifluoride, the reaction is finished, a hydrofluoric acid aqueous solution is added to form a salt, the layering is extracted, and the tri-tert-butylphosphonium - tetrafluoroborate is obtained through recrystallization. The method is simple, feasible, safe and environment-friendly. When the tert-butyl Grignard reagent is reacted with the phosphorus trihalide, the tert-butyl phosphorus intermediate acts in the reaction process by adding the boron trifluoride complex, thereby improving the halogen ion release property, improving the tri-substituted product to 94 - 95%, the reaction yield 85 - 87% and the organic solvent can be recycled.
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Paragraph 0017-0018; 0020-0021; 0023-0024; 0026-0027; ...
(2021/11/26)
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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.
- García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
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supporting information
(2022/01/04)
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- Method for synthesizing tri-tert-butyl phosphine
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The invention discloses a method for synthesizing tri-tert-butyl phosphine, belonging to the field of organic synthesis. Tri-tert-butyl phosphine is synthesized from tert-butyl bromide and calcium phosphide in anhydrous and anaerobic atmosphere under the catalyst action of a nickel catalyst. Compared with the prior art, the invention has the advantages of mild reaction conditions, simple operation, high yield, simple and easy-to-obtain raw materials, reduced production cost and being suitable for industrial production.
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Paragraph 0008-0011
(2019/04/26)
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- Phosphorescent OLED and hole transporting materials for phosphorescent OLEDs
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The present invention relates to phosphorescent organic light-emitting diodes (OLEDs) comprising a hole-transporting or a hole-transporting and an electron-blocking layer comprising an N,N,N',N'-tetraaryl-phenylene-3,5-diamine or an N,N,N',N'-tetraaryl-1,1'-biphenyl-3,3'-diamine matrix compound and to new N,N,N',N'-tetraarylsubstituted m-arylene diamine compounds useful as hole-transporting and electron-blocking layer matrices in phosphorescent OLEDs.
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(2014/05/07)
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- Reactivity and Moessbauer spectroscopic characterization of an Fe(IV) ketimide complex and reinvestigation of an Fe(IV) norbornyl complex
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Thermolysis of Fe(Ni=CtBu2)4 (1) for 8 h at 50 °C generates the mixed valent Fe(III)/Fe(II) bimetallic complex Fe2(Ni=CtBu2)5 (2) in moderate yield. Also formed in this reaction
- Lewis, Richard A.,Smiles, Danil E.,Darmon, Jonathan M.,Stieber, S. Chantal E.,Wu, Guang,Hayton, Trevor W.
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p. 8218 - 8227
(2013/08/23)
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- Bis-boranes in the frustrated Lewis pair activation of carbon dioxide
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Using a frustrated Lewis pair approach, the 1,1-bis-(C6F 5)2BOB(C6F5)2 is shown to bind CO2 in a monodentate fashion, while the bis-boranes (X 2B)2CCMe2 (X = Cl, C6F5) give bidentate chelation of CO2 affording unique heterocycles.
- Zhao, Xiaoxi,Stephan, Douglas W.
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p. 1833 - 1835
(2011/04/17)
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- Use of phosphonium salts in coupling reactions and process for their manufacture
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The object of the present invention is the use of phosphonium salts in coupling reactions, and a method for their presentation.
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Page/Page column 8-9
(2009/02/10)
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- PROCESS FOR PRODUCING TERTIARY PHOSPHINE HAVING BULKY HYDROCARBON GROUP BONDED
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The present invention provides a production process by which tertiary phosphine with an attached sterically bulky hydrocarbon group, said tertiary phosphine being useful as a ligand of a transition metal catalyst in organic synthesis reactions, can be produced in a high yield and with high purity on an industrial scale through simple and safe operations. The present invention comprises allowing a dialkylphosphinous halide to react with a Grignard reagent in the presence of a copper compound in an amount corresponding to 0.1 to 5% by mol based on the dialkylphosphinous halide to produce tertiary phosphine represented by the following formula (3) : wherein R1 and R2 are each a tertiary hydrocarbon group of 4 to 13 carbon atoms, and R3 is an alkyl group, an alkenyl group, an aryl group or the like.
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- Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes
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Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3/
- Roy, Amy H.,Hartwig, John F.
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p. 13944 - 13945
(2007/10/03)
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- Process for preparing tertiary phosphines
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The invention relates to a process for synthesizing tertiary phosphines by reacting halophosphines with organomagnesium compounds in the presence of copper compounds and optionally of salts.
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- An acidity scale for phosphorus-containing compounds including metal hydrides and dihydrogen complexes in THF: Toward the unification of acidity scales
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More than 70 equilibrium constants K between acids and bases, mainly phosphine derivatives, have been measured in tetrahydrofuran (THF) at 20 °C by 1H and/or 31P NMR. The acids were chosen or newly synthesized in order to cover the wide pK(α)(THF) range of 5-41 versus the anchor compound [HPCy3]BPh4 at 9.7. These pK(α)(THF) values are approximations to absolute, free ion pK(a)(THF) and are obtained by crudely correcting the observed K for 1:1 ion-pairing effects by use of the Fuoss equation. The acid/base compounds include 14 phosphonium/phosphine couples, 17 cationic hydride/neutral hydride couples, 9 neutral polyhydride/anionic hydride couples, 14 dihydrogen/hydride couples, and 4 other nitrogen- and phosphorus-based acids. The effects on pK(α) of the counterions BAr'4- and BF4- vs BPh4- and [K(2,2,2-crypt)]+ versus [K(18-crown-6)+ are found to be minor after correcting for differences in inter-ion distances in the ion-pairs involved. Correlations with v(M-H) noted here for the first time suggest that destabilization of M-H bonding in the conjugate base hydride is an important contributor to hydride acidity. It appears that Re-H bonding in the anions [ReH6(PR3)2- is greatly weakened by small increases in the basicity of PR3, resulting in a large increase in the pK(α) of the conjugate acid ReH7(PR3)2. Correlations with other scales allow an estimate of the pK(α)(THF) values of more than 1000 inorganic and organic acids, 20 carbonyl hydride complexes, 46 cationic hydrides complexes, and dihydrogen gas. Therefore, many new acid-base reactions can be predicted and known reactions explained. THF, with its low dielectric constant, disfavors the ionization of neutral acids HA over HB+ and therefore separate lines are found for pK(α)(THF)(HA) and pK(α)(THF)(HB+) when plotted against pK(a)(DMSO) or pK(a)(MeCN). The crystal structure of [Re(H)2(PMe3)5]BPh4 is reported.
- Abdur-Rashid, Kamaluddin,Fong, Tina P.,Greaves, Bronwyn,Gusev, Dmitry G.,Hinman, Justin G.,Landau, Shaun E.,Lough, Alan J.,Morris, Robert H.
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p. 9155 - 9171
(2007/10/03)
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- Method for manufacturing acryloxypropysilane
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A method to manufacture acryloxypropylsilane to a high degree of purity is achieved by hydrosilation of (A) allyl acrylate or allyl methacrylate by (B) a hydrosilane compound, using (C) a platinum-containing compound as the catalyst and (D) an organic phosphorus compound as the promoter. The acryloxypropylsilane product is expressed by General Formula I where R1 represents a hydrogen or methyl group, R2 represents a hydrolyzable group, R3 represents an aryl, alkenyl or aryl group of carbon number 1-12, and n is 0, 1, 2, or 3.
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- TELLUROPHOSPHONIUM-KATIONEN
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Tellurophosphoranes R3P=Te (R = CH3, i-C3H7, n-C4H9, t-C4H9, N(CH3)2) 1 react with CH3I to give the cations + 2.Te(CH3)2 and R3P are formed on treatment of 2 with LiCH3.
- Kuhn, Norbert,Schumann, Hans
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p. 199 - 202
(2007/10/02)
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- The Reaction of Tri-t-butylphosphane and Tri-t-butylarsane with Selenium and Tellurium: Formation of Inert and Labile Chalcogenophosphoranes and -arsoranes
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The reactions of tri-t-butylphosphane 1 with selenium and tellurium proceed quantitatively with formation of seleno- and the telluro-tri-t-butylphosphorane, respectively (3,4).Tri-t-butylarsane 2 reacts with selenium to give seleno-tri-t-butylarsorane (5), but no significant interaction is observed between 2 and elemental tellurium. 1H and 31P NMR spectra provide evidence for rapid tellurium transfer between telluro-tri-t-butylphosphorane (4) and tri-t-butylphosphane (1), tri-t-butylarsane (2) or tris(dimethylamino)phosphane.Selenium transfer between seleno-tri-t-butylarsorane (5) and tri-t-butylarsane (2) leads to 1H and 13C NMR line broadening.Vibrational spectra of t-Bu3E-Y (3: E=P, Y=Se; 4: E=P, Y=Te; 5: E=As, X=Se) indicate coupling of E-C and E-Y stretching vibrations in 3 and 4. - Keywords: Tellurium Transfer, NMR Spectra, IR Spectra, MS, Selenium Transfer
- Mont, Wolf-W. du
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p. 1453 - 1456
(2007/10/02)
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- Preparation and Characterization of Trichlorostannylplatinum Hydride Complexes Containing Sterically Bulky Phosphine Ligands
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Trichlorostannylplatinum(II) hydride complexes containing sterically bulky phosphine ligands, trans-(R3P)2PtH(SnCl3)(1) R3P=t-BuPh2P, Cy3P, t-Bu2MeP) have been prepared by the reaction of hydrated tin(II) dichloride with respective chloro-platinum hydride complexes.A trans-geometry has been assigned for the complexes (1) on the basis of 1H and 31P NMR spectral studies.An unusually large magnitude of two-bond tin-hydrogen coupling (JSn-H ca.1598-1682 Hz) has been observed in the PMR spectra of these complexes.From the reaction of tin (II) dichloride with trans-(t-Bu3P)2PtH(Cl), surprisingly, a complex corresponding to (t-Bu3P)PtCl(SnCl3) (3) has been obtained.In solutions, one of the tri-t-butylphosphines of 3, undergoes intramolecular metalation generating a new, probably a platinum (IV) complex, .
- Goel, Anil B.,Goel, Sarla
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p. 980 - 982
(2007/10/02)
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- Molecular structures of phosphorus compounds. 6. An electron diffraction study of tert-butylfluorophosphines ButnPF3-n (n = 1, 2, 3)
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The geometric structures of tert-butyldifluorophosphine, di-tert-butylfluorophosphine, and tri-tert-butylphosphine have been determined in the gas phase by electron diffraction. Successive substitution of fluorine atoms by tert-butyl groups results in the lengthening of both P-F and P-C bond distances. The P-F bond lengths increase from 1.589 (3) ? in ButPF2 to 1.619 (7) ? in But2PF. The P-C bond lengths increase even more strongly from 1.822 (12) ? in ButPF2 to 1.859 (6) A in But2PF to 1.919 (5) ? in But3P. The bond angles at the phosphorus atom follow the opposite trend. The CPF angle decreases from 99.0 (0.6)° in ButPF2 to 96.0 (2.0)° in But2PF, and the CPC angle decreases from 113.8 (1.9)° in But2PF to 109.9 (0.7)° in But3P. The geometric parameters and the configuration of the tert-butyl groups are given in the paper. The electron diffraction results are compared with results obtained by CNDO/2 calculations. The effect of steric strain on the geometry caused by the bulky tert-butyl groups is discussed.
- Oberhammer, Heinz,Schmutzler, Reinhard,Stelzer, Othmar
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p. 1254 - 1258
(2007/10/05)
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