33513-42-7Relevant articles and documents
Bulk gold-catalyzed oxidations of amines and benzyl alcohol using amine N-oxides as oxidants
Klobukowski, Erik R.,Angelici, Robert J.,Woo, L. Keith
, p. 161 - 167 (2012)
Bulk gold powder (～50 μm) catalyzes the oxidative dehydrogenation of amines to give imines using amine N-oxides (R3N-O) as the oxidant. The reaction of dibenzylamine (PhCH2-NH-CH2Ph) with N-methylmorpholine N-oxide (NMMO) in the presence of gold powder at 60 °C produced N-benzylidenebenzylamine (PhCH=N-CH2Ph) in 96% yield within 24 h. Benzyl alcohol was oxidized by NMMO to benzaldehyde in >60% yield in the presence of gold powder. Although O2 was previously shown to oxidize amines in the presence of bulk gold, it is surprising that gold is also capable of catalyzing the oxidation of amines using amine oxides, which are chemically so different from O2. Graphical Abstract: [Figure not available: see fulltext.]
Water-soluble trialkylphosphine-ruthenium(II) complexes as efficient catalysts for hydrogenation of supercritical carbon dioxide
Kayaki, Yoshihito,Suzuki, Tomoyuki,Ikariya, Takao
, p. 1016 - 1017 (2001)
A water-soluble ruthenium(II) complex bearing tris(hydroxymethyl)phosphine, RuCl2[PH(CH2OH)2]2-[P(CH 2OH)3]2, is highly effective for the catalytic hydrogenation of supercritical carbon dioxide (scCO2) under scCO2-H2O multi-phasic conditions.
Catalytic Formylation of Primary and Secondary Amines with CO2 and H2 Using Abundant-Metal Catalysts
Affan, Mohammad A.,Jessop, Philip G.
, p. 7301 - 7305 (2017)
Catalytic hydrogenation of CO2 is an efficient and selective way to prepare formic acid derivatives, but most of the highly active catalysts used for this purpose require precious metals. In this study, in situ abundant-metal complexes have been evaluated as potential catalysts for CO2 hydrogenation to prepare formamides, including N-formylmorpholine, 2-ethylhexylformamide, and dimethylformamide, from the corresponding amines. From these initial screening results, the most active catalysts for these reactions were found to be MX2/dmpe in situ catalysts (M = Fe(II), Ni(II); X = Cl-, CH3CO2-, acac- dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. The optimal reaction conditions were found to be 100-135 °C and a total pressure of 100 bar. Morpholine was formylated with a TON value of up to 18000, which is the highest TON for the hydrogenation of CO2 to formamides using any abundant-metal-phosphine complex. With an appropriate selection of catalyst and reaction conditions, >90-98% conversion of amine to formamide could be achieved.
Solvate sponge crystals of (DMF)3NaClO4: reversible pressure/temperature controlled juicing in a melt/press-castable sodium-ion conductor
Prakash, Prabhat,Ardhra, Shylendran,Fall, Birane,Zdilla, Michael J.,Wunder, Stephanie L.,Venkatnathan, Arun
, p. 5574 - 5581 (2021)
A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (DMF)3NaClO4and (DMF)2NaClO4(DMF =N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)3NaClO4to generate (DMF)2NaClO4. The process reverses upon the release of pressure or cooling. Simulations reveal the mechanism of crystal “juicing,” as well as melting. In particular, cation-solvent clusters form a chain of octahedrally coordinated Na+-DMF networks, which have perchlorate ions present in a separate sublattice space in 3?:?1 stoichiometry. Upon heating and/or pressing, the Na+?DMF chains break and the replacement of a DMF molecule with a ClO4?anion per Na+ion leads to the conversion of the 3?:?1 stoichiometry to a 2?:?1 stoichiometry. The simulations reveal the anisotropic nature of pressure induced stoichiometric conversion. The results provide molecular level understanding of a solvate sponge crystal with novel and desirable physical castability properties for device fabrication.
The interaction of N,N,N′,N′-tetramethylphosphoric triamide with chloral: Phosphorus-nitrogen fission products and the X-ray crystal structure of N,N,N′,N′-tetramethyl-n″-(2,2,2-trichloro-1- dimethylaminoethyl)phosphoric triamide
Hudson, Harry R.,McPartlin, Mary,Ma Vrommatis, Christakis N.,Pianka, Max
, p. 39 - 48 (1997)
The interaction of N,N,N′,N′-tetramethylphosphoric triamide with chloral gives dimethylformamide, chloroform, and a complex mixture of phosphorus-containing products, amongst which N,N,N′,N′-tetramethyl-N″-(2,2,2-trichloro-1- dimethylaminoethyl)phosphoric triamide was characterized by single crystal X-ray diffraction. Dimethylamino(imino)oxophosphorane is postulated as a tricoordinate phosphorus (V) by-product, which undergoes oligomerization or reaction with other components of the reaction system.
Reversible Homogeneous Catalysis of Carbon Dioxide Hydrogenation/Reduction at Room Temperature and Low Pressures
Schreiner, Serge,Yu, James Y.,Vaska, Lauri
, p. 602 - 603 (1988)
The reaction between CO2, H2, and Me2NH to yield HC(O)NMe2 and H2O is catalysed by (dppm=Ph2PCH2PPh2) under unprecedented mild conditions in toluene solution, and the catalysis is readily reversible.
Heptanuclear zinc carboxylate complex: New supramolecular building unit and unique supramolecular architecture
Reger, Daniel L.,Debreczeni, Agota,Pascui, Andrea E.,Smith, Mark D.
, p. 1317 - 1322 (2013)
The reaction of the bifunctional ligand (1,8-naphthalimido)propanoate (LC2-), containing a carboxylate group for metal bonding and a 1,8-naphthalimide group for π···π stacking interactions, with Zn(O2CCH3)2(H 2O)2 yields a novel heptanuclear complex [Zn 7(O)2(LC2)10(DMF)2]. In the solid-state structure, a central zinc(II) cation is linked to six terminal zinc(II) cations by ten bridging carboxylate ligands and two μ4-O ions forming a vertex shared bitetrahedron, a new type of secondary building unit (SBU). The heptanuclear units are organized into a complex three-dimensional architecture by π···π stacking interactions of the 1,8-naphthalimide groups. Eight of the naphthalimide rings on each heptanuclear unit form π···π stacking interactions with rings on eight adjacent units generating a unique single linked three-dimensional architecture. The TGA data indicate this structure is robust and luminescent studies show the solid emits in the green region.
Synthesis of N,N-dimethylformamide from carbon dioxide in aqueous biphasic solvent systems
Kuhlmann,Schmitz,Ha?mann,Prüllage,Behr
, p. 90 - 96 (2017)
This paper presents the homogeneous catalyzed hydrogenation of carbon dioxide to N,N-dimethylformamide (DMF) with an in-situ generated ruthenium catalyst based on RuCl3?×?H2O and the phosphine ligand 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl (BISBI). Investigations showed that the complex formation of an active species requires the presence of an amine. The catalyst was recycled by immobilization in a nonpolar alcoholic solvent while the formed product was extracted in-situ into the aqueous phase. The self-assembling reaction system showed stability for 10 recycling runs without a significant loss of activity resulting in an average yield of 31% DMF at 40?bar and 140?°C without the occurrence of any byproducts. Furthermore, a combination of the developed reaction system with ternary amines enables the application of wash amine solutions as carbon dioxide carrier.
Kinetics and mechanism of complex formation of nickel(II) with tetra-N-alkylated cyclam in N,N-dimethylformamide (DMF): Comparative study on the reactivity and solvent exchange of the species Ni(DMF)62+ and Ni(DMF)5Cl
Elias, Horst,Schumacher, Ruediger,Schwamberger, Joerg,Wittekopf, Thorsten,Helm, Lothar,Merbach, Andre E.,Ulrich, Stefan
, p. 1721 - 1727 (2000)
13C NMR was used to study the rate of DMF exchange in the nickel(II) cation Ni(DMF)62+ and in the monochloro species Ni(DMF)5Cl+ with 13C-labeled DMF in the temperature range of 193-395 K i
Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2 Hydrogenation to Methanol and Catalyst Inhibition
Mathis, Cheryl L.,Geary, Jackson,Ardon, Yotam,Reese, Maxwell S.,Philliber, Mallory A.,Vanderlinden, Ryan T.,Saouma, Caroline T.
, p. 14317 - 14328 (2019)
The hydrogenation of CO2 in the presence of amines to formate, formamides, and methanol (MeOH) is a promising approach to streamlining carbon capture and recycling. To achieve this, understanding how catalyst design impacts selectivity and performance is critical. Herein we describe a thorough thermochemical analysis of the (de)hydrogenation catalyst, (PNP)Ru-Cl (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine; Ru = Ru(CO)(H)) and correlate our findings to catalyst performance. Although this catalyst is known to hydrogenate CO2 to formate with a mild base, we show that MeOH is produced when using a strong base. Consistent with pKa measurements, the requirement for a strong base suggests that the deprotonation of a six-coordinate Ru species is integral to the catalytic cycle that produces MeOH. Our studies also indicate that the concentration of MeOH produced is independent of catalyst concentration, consistent with a deactivation pathway that is dependent on methanol concentration, not equivalency. Our temperature-dependent equilibrium studies of the dearomatized congener, (*PNP)Ru, with various H-X species (to give (PNP)Ru-X; X = H, OH, OMe, OCHO, OC(O)NMe2) reveal that formic acid equilibrium is approximately temperature-independent; relative to H2, it is more favored at elevated temperatures. We also measure the hydricity of (PNP)Ru-H in THF and show how subsequent coordination of the substrate can impact the apparent hydricity. The implications of this work are broadly applicable to hydrogenation and dehydrogenation catalysis and, in particular, to those that can undergo metal-ligand cooperativity (MLC) at the catalyst. These results serve to benchmark future studies by allowing comparisons to be made among catalysts and will positively impact rational catalyst design.
