13689-19-5Relevant academic research and scientific papers
Facile purification of C60O-containing [60]fullerene using trialkylphosphines at room temperature
Hashiguchi, Masahiko,Nagata, Koichi,Tanaka, Katsutomo,Matsuo, Yutaka
, p. 643 - 646 (2012)
A novel method using trialkylphosphines is reported for the facile purification of [60]fullerene containing C60O. When tri-n-butylphosphine and tri-n-octylphosphine were added to unrefined C 60 (ca. 97% purity) in 1,2,4-trimethylbenzene, C60O was readily reduced to give high-purity C60 (>99% purity). The best results were obtained for a high concentration (>1.0 wt %) of unrefined fullerene treated with tri-n-octylphosphine at room temperature. This method is simple and fast in comparison with conventional alumina chromatography, and thus, it is well-suited to industrial-scale separation.
Oxidation of phosphines by supercritical nitrous oxide
Poh, Scott,Hernandez, Raquel,Inagaki, Mayuko,Jessop, Philip G.
, p. 583 - 585 (1999)
(Matrix presented) Despite its reputation for lack of reactivity at moderate temperatures, nitrous oxide is capable of oxidizing at least one class of organic compounds, the phosphines, at temperatures at or below 100°C. The use of supercritical N2O as both the solvent and the reactant simplifies the isolation of the products and allows one to avoid the use of flammable liquid solvents.
Dicopper μ?oxo, μ?nitrosyl complex from the activation of nO or nitrite at a dicopper center
Tao, Wenjie,Bower, Jamey K.,Moore, Curtis E.,Zhang, Shiyu
, p. 10159 - 10164 (2019)
Treatment of a dicopper(I,I) complex with nitric oxide produces a dicopper μ-oxo, μ-nitrosyl complex [LCu2(μ-O)(μ-NO)]2+, representing the first structurally characterized μ-oxo, μ-nitrosyl metal complex. This compound can also be synthesized from the reaction of nitrite with an [LCuIICuI]3+ synthon. Full characterization of the thermal-sensitive [LCu2(μ-O)(μ-NO)]2+ complex with IR, EPR, and X-ray crystallography suggests a localized mixed-valent CuIII, CuII, O2?, NO? formulation. The [Cu2(μ-O)(μ-NO)]2+ core efficiently oxidizes exogenous substrates, such as phosphine, cyclohexadienes, and isochroman to afford phosphine oxide, benzene, and 1-isochromanone. Since both nitrite and nitric oxide are proposed oxidants in denitrifying methane oxidation, the oxidative reactivity of [Cu2(μ-O)(μ-NO)]2+ core is potentially relevant to anaerobic methane oxidation observed in methanotro hic archaea
N2O oxidation of phosphines catalyzed by low-valent nickel complexes
Yamada, Tohru,Suzuki, Kyosuke,Hashimoto, Kentaro,Ikeno, Taketo
, p. 1043 - 1044 (1999)
In the presence of a catalytic amount of the nickel(0) complex derived from Ni(acac)2 or NiCl2 with DIBAL or BuLi, nitrous oxide (N2O) was captured and activated to oxidize phosphine(III) into the corresponding phosphine oxide. Bidentate phosphines, for example, 1,3-bis(diphenyl-phosphino)propane (dppp), were employed as effective ligands for N2O; oxidation and were recovered after the reaction.
New hydrogen bonding motifs of phosphine oxides with a silanediol, a phenol, and chloroform
Kharel, Sugam,Bhuvanesh, Nattamai,Gladysz, John A.,Blümel, Janet
, p. 215 - 219 (2019)
Three new hydrogen bonding motifs of phosphine oxides involving a silanol, a phenol, and chloroform are described. The single crystal X-ray structures, in combination with the NMR and IR data of the new adducts Ph3PO?HOSiPh2OSiPhsub
Stereoselective synthesis of the diazonamide a macrocyclic core
Mutule, Ilga,Joo, Beomjun,Medne, Zane,Kalnins, Toms,Vedejs, Edwin,Suna, Edgars
, p. 3058 - 3066 (2015)
Stereoselective synthesis of the right-hand heteroaromatic macrocycle of diazonamide A features C16-C18 bond formation in the Suzuki-Miyaura cross-coupling and atropodiastereoselective Dieckmann-type macrocyclization as key steps. The Suzuki-Miyaura cross
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Olefin Metathesis, p-Cresol, and the Second Generation Grubbs Catalyst: Fitting the Pieces
Swart, Marthinus R.,Twigge, Linette,Erasmus, Elizabeth,Marais, Charlene,Bezuidenhoudt, Barend C. B.
, p. 1752 - 1762 (2021/05/06)
p-Cresol as additive to the Grubbs second generation catalyst (GII) allows the cross-metathesis of acrylates with prop-1-en-1-ylbenzenes under conditions that only give the prop-1-en-1-ylbenzene self-metathesis product in the absence of cresol. NMR and IR spectroscopy, MALDI-TOF MS and XPS supported the formation of a ruthenium benzylidene with hydrogen bonds between p-cresol and the chloride ligands of GII. XPS furthermore confirmed p-cresol to increase the binding energies of the GII Ru 3d5/2, 3d3/2, 3p3/2 and 3p1/2 photoelectron lines, whereas 1H NMR spectroscopy indicated the carbene carbon and hydrogen to be shielded. It is thus postulated that p-cresol allows for more facile interaction between electron-deficient compounds and the ruthenium benzylidene by decreasing the electron density on the metal center and increasing the electron density on the carbene.
EUROPIUM COMPLEX
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Paragraph 0248-0250, (2020/11/23)
To provide europium complexes having high photostability. A europium complex expressed with the following formula (A): {wherein, RA and RB are independently a cyclic alkyl group with 3 to 10 carbons, respectively, and RC is a cyclic alkyl group with 3 to 10 carbons or a phenyl group expressed with the following formula (B): (wherein, XA, XB, AC, XD and XE independently represent a hydrogen atom; a fluorine atom; an alkyl group with 1 to 3 carbon(s); an alkyloxy group with 1 to 3 carbon(s); an aryloxy group with 6 to 10 carbons; a fluoroalkyl group with 1 to 3 carbon(s); a fluoroalkyloxy group with 1 to 3 carbon(s); or a phenyl group that may be substituted with a fluorine atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a fluorophenyl group, a hydroxyl group or a cyano group, respectively); RA is a cyclic alkyl group with 3 to 10 carbons; RB and RC are a phenyl group expressed with the formula (B), provided, however, that a case where RA a cyclohexyl group, and, RB and RC are a phenyl group is excluded; or RA, RB and RC independently represent an ortho-substituted phenyl group expressed with the following formula (Ba): (wherein, XE represents a hydrogen atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a naphthyl group that may be substituted with a fluorine atom, a pyridyl group that may be substituted with a fluorine atom, or a phenyl group that is expressed with a formula (C): [wherein, ZA, ZC and ZE independently represent a hydrogen atom, a fluorine atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a phenyl group that may be substituted with a fluorine atom, a hydroxyl group or a cyano group; ZB and ZD independently represent a hydrogen atom or a fluorine atom, respectively], provided, however, that a case where RA, RB and RC are all a phenyl group is excluded), respectively; RD represents a hydrogen atom, a deuterium atom or a fluorine atom; WA and WB independently represent an alkyl group with 1 to 6 carbon(s), a fluoroalkyl group with 1 to 6 carbon(s), a phenyl group, a 2-thienyl group or a 3-thienyl group; and ‘n’ represents an integer of 1 to 3}.
Flat and Efficient H CNN and CNN Pincer Ruthenium Catalysts for Carbonyl Compound Reduction
Giboulot, Steven,Baldino, Salvatore,Ballico, Maurizio,Figliolia, Rosario,P?thig, Alexander,Zhang, Shuanming,Zuccaccia, Daniele,Baratta, Walter
supporting information, p. 1127 - 1142 (2019/03/14)
The bidentate HCNN dicarbonyl ruthenium complexes trans,cis-[RuCl2(HCNN)(CO)2] (1-3) and trans,cis-[RuCl2(ampy)(CO)2] (1a) were prepared by reaction of [RuCl2(CO)2]n with 1-[6-(4′-methylphenyl)pyridin-2-yl]methanamine, benzo[h]quinoline (HCNN), and 2-(aminomethyl)pyridine (ampy) ligands. Alternatively, the derivatives 1-3 were obtained from the reaction of RuCl3 hydrate with HCO2H and HCNN. The pincer CNN cis-[RuCl(CNN)(CO)2] (4) was isolated from 1 by reaction with NEt3. The monocarbonyl complexes trans-[RuCl2(HCNN)(PPh3)(CO)] (5-7) were synthesized from [RuCl2(dmf)(PPh3)2(CO)] and HCNN ligands, while the diacetate trans-[Ru(OAc)2(HCNN)(PPh3)(CO)] (8) was obtained from [Ru(OAc)2(PPh3)2(CO)]. Carbonylation of cis-[RuCl(CNN)(PPh3)2] with CO afforded the pincer derivatives [RuCl(CNN)(PPh3)(CO)] (9-11). Treatment of 9 with Na[BArf]4 and PPh3 gave the cationic complex trans-[Ru(CNN)(PPh3)2(CO)][BArf4] (12). The dicarbonyl derivatives 1-4, in the presence of PPh3 or PCy3, and the monocarbonyl complexes 5-12 catalyzed the transfer hydrogenation (TH) of acetophenone (a) in 2-propanol at reflux (S/C = 1000-100000 and TOF up to 100000 h-1). Compounds 1-3, with PCy3, and 6 and 8-10 were proven to catalyze the TH of carbonyl compounds, including α,β-unsaturated aldehydes and bulky ketones (S/C and TOF up to 10000 and 100000 h-1, respectively). The derivatives 1-3 with PCy3 and 5 and 6 catalyzed the hydrogenation (HY) of a (H2, 30 bar) at 70 °C (S/C = 2000-10000). Complex 5 was active in the HY of diaryl ketones and aryl methyl ketones, leading to complete conversion at S/C = 10000.
