29938-19-0Relevant academic research and scientific papers
Synthesis and characterization of Ni(II) and Pd(II) complexes bearing achiral and chiral bidentate aminophosphine ligands
Benito-Garagorri, David,Mereiter, Kurt,Kirchner, Karl
, p. 527 - 540 (2007)
The synthesis of a range of achiral and chiral bidentate aminophosphine ligands and their complexes with nickel(II) and palladium(II) has been investigated. The ligands and the complexes have been characterized by NMR spectroscopy, and X-ray structures of representative compounds have been determined. In addition, DFT calculations have been performed to investigate different geometries of the nickel(II) complexes in the solid state and in solution.
Valorization of furfural using ruthenium (II) complexes containing phosphorus-nitrogen ligands under homogeneous transfer hydrogen condition
Aguirre, Pedro,Aranda, Braulio,López, Vicente,Moya, Sergio A.,Parra-Melipán, Sebastián,Valdebenito, Gonzalo
, (2021/08/10)
In this paper, we report the catalytic activity of a series of ruthenium (II) complexes containing phosphorus-nitrogen bidentated (P-N) ligands in the hydrogenation of furfural via hydrogen transfer reaction using two hydrogen donor sources: 2-propanol in basic medium and formic acid under mild conditions. The results showed that all the ruthenium complexes studied are catalytically active in the hydrogenation of furfural by hydrogen transfer reaction; they showed 100% conversion with both hydrogen sources. However, selectivities towards the formation of furfuryl alcohol were better when formic acid was used. It was also found that the reaction studied in a basic medium competes with the Cannizzaro reaction, obtaining furfuryl alcohol and furoic acid in a 70/30 ratio; on the other hand, using formic acid as the hydrogen source yields furfuryl alcohol with 100% selectivity. Although formic acid can be used as a hydrogen source successfully. The optimal substrate/acid ratio was found to be 1:1, as a higher concentration of formic acid can cause catalyst decomposition. The yielded products, furfuryl alcohol and furoic acid, obtained from renewable sources, have multiple applications in the organic chemical industry, replacing or complementing similar fossil-derived products.
Catalytic activity of a new Ru(ii) complex for the hydrogen transfer reaction of acetophenone and: N -benzylideneaniline: Synthesis, characterization and relativistic DFT approaches
Pérez-Zú?iga,Negrete-Vergara,Yá?ez, Mauricio,Aguirre, Pedro,Zú?iga, César A.,Cantero-López, Plinio,Arratia-Pérez, Ramiro,Moya, Sergio A.
, p. 10545 - 10553 (2019/07/08)
The synthesis and characterization of a new ruthenium(ii) complex containing a hemilabile P^N-ligand are reported. The catalytic activity of this complex was evaluated in the hydrogen transfer reaction of acetophenone and N-benzylideneaniline achieving conversions around 35 and 96% respectively. Condensed Fukui functions in a relativistic DFT scheme show that the regions for the electrophilic (f-) and nucleophilic (f+) attack are Cl- in the axial position, regions belonging to the P^N ligand and the metal center. The lability of the ligands is determined using different theoretical approaches like Morokuma-Ziegler energy decomposition analysis combined with the Extended Transition State with Natural Orbitals of Chemical Valence (ETS-NOCV). The major lability for the -Cl ligand (protic environment) is ideal for designing a new ruthenium hydride complex, suitable for catalytic applications. The σ-donation determines the degree of covalence of the chemical bond involving a lower trend to dissociate, as is the case of the P^N-ligand. The most important excitation energies appear in the region between 250 and 410 nm and are assigned to ligand to ligand charge transfer (LLCT) and metal to ligand charge transfer (MLCT) transitions.
Method for preparing primary amide from olefin, carbon monoxide and ammonia gas
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Paragraph 0013; 0014; 0015; 0022; 0023; 0024, (2018/06/15)
The invention discloses a method for preparing primary amide from olefin, carbon monoxide and ammonia gas. According to the method, olefin, carbon monoxide and ammonia gas are used as raw materials for preparation of primary amide under the action of a catalyst composed of phosphine ligand and a rhodium compound; the used phosphine ligand can guarantee that the rhodium compound uses as the catalyst effectively catalyzes carboamidation of olefin, so high-yield production of primary amide can be realized; and the phosphine ligand also contains N-heteroatoms or/and O-heteroatoms or/and S-heteroatoms. The method is a one-pot synthetic method and is simple in synthesis steps; high yield of primary amide is realized in preparation of primary amide from olefin, carbon monoxide and ammonia gas through carboamidation under the action of the catalyst composed of the phosphine ligand and the rhodium compound; and the catalyst has good catalysis performance and stable service life.
Six-coordinate high-spin iron(ii) complexes with bidentate PN ligands based on 2-aminopyridine-new Fe(ii) spin crossover systems
Holzhacker, Christian,Calhorda, Maria Jose,Gil, Adria,Carvalho, Maria Deus,Ferreira, Liliana P.,Stoeger, Berthold,Mereiter, Kurt,Weil, Matthias,Mueller, Danny,Weinberger, Peter,Pittenauer, Ernst,Allmaier, Guenter,Kirchner, Karl
, p. 11152 - 11164 (2014/07/21)
Several new octahedral iron(ii) complexes of the type [Fe(PN R-Ph)2X2] (X = Cl, Br; R = H, Me) containing bidentate PNR-Ph (R = H, Me) (1a,b) ligands based on 2-aminopyridine were prepared. 57Fe Moess
Synthesis, structure and bactericide activity of (aminophosphane)gold(I) thiolate complexes
Fillat, Maria F.,Gimeno, M. Concepcion,Laguna, Antonio,Latorre, Encarnacion,Ortego, Lourdes,Villacampa, M. Dolores
scheme or table, p. 1487 - 1495 (2011/06/20)
Reaction of the aminophosphane ligands 2-(diphenylphosphanylamino) pyridine (Ph2PNHpy, 1) and 3-(diphenylphosphanylamino)-1,2,4-triazole [Ph2PNH(Htrz), 2] with the gold(I) compound [AuCl(tht)] (tht = tetrahydrothiophene) gave the com
New iridium catalysts for the efficient alkylation of anilines by alcohols under mild conditions
Michlik, Stefan,Kempe, Rhett
supporting information; experimental part, p. 13193 - 13198 (2011/02/24)
The synthesis of eight new iridium complexes containing anionic P,N ligands is described. These complexes have been investigated as catalysts for amine alkylation reactions, resulting in a highly active catalyst for the selective monoalkylation of anilines with primary alcohols, under mild reaction conditions. Nearly quantitative conversion was observed at 70 °C with a catalyst loading as low as 0.05 mol % iridium. Selective amine alkylation: The synthesis of eight new iridium complexes containing anionic P,N ligands (see image) is described. These new complexes were used as highly active catalysts for the selective monoalkylation of anilines with primary alcohols, and gave nearly quantitative conversion under mild reaction conditions.
Isoprene polymerization with aminopyridinato ligand supported rare-earth metal complexes. Switching of the regio- and stereoselectivity
Yang, Yi,Lv, Kui,Wang, Lingfang,Wang, Yang,Cui, Dongmei
supporting information; experimental part, p. 6150 - 6152 (2010/10/20)
The highly cis-1,4, trans-1,4 and 3,4-selective polymerizations of isoprene were successfully regulated by simply modifying the auxiliary ligands, metal centres and initiation groups of rare-earth metal complexes and cocatalysts.
Synthesis and characterization of ruthenium p-cymene complexes bearing bidentate P-N and E-N ligands (E = S, Se) based on 2-aminopyridine
Lackner-Warton, Wolfgang,Tanaka, Shinji,Standfest-Hauser, Christina M.,?ztopcu, ?zgür,Hsieh, Jen-Chieh,Mereiter, Kurt,Kirchner, Karl
scheme or table, p. 3097 - 3102 (2011/01/08)
The syntheses and characterization of a series of cationic of Ru(II) halfsandwich complexes of the types [Ru(η6-p-cymene) (κ2(P,N)-PN)Cl]+ (PN = N-diphenylphosphino-2- aminopyridine, N-di-iso-propylphosphino-2-aminopyridine, 2-[(2-pyridyl)amino] dibenzo[d,f][1,2,3]dioxaphosphepine, N-(diisopropylphosphino)-2,6- diaminopyridine) and [Ru(η6-p-cymene)(κ2(E,N)- EN)Cl]+ (EN = N-(2-pyridinyl)amino-diphenylphosphine sulfide, N-(2-pyridinyl)amino-diisopropylphosphine sulfide, N-(2-pyridinyl)amino- diphenylphosphine selenide, N-(2-pyridinyl)amino-diisopropylphosphine selenide) is described. Some of these complexes were tested as precatalysts for the transfer hydrogenation of acetophenone to give 1-phenyl ethanol.
Methoxycarbonylation of olefins catalyzed by palladium complexes bearing P,N-donor ligands
Aguirre, Pedro A.,Lagos, Carolina A.,Moya, Sergio A.,Zuniga, Cesar,Vera-Oyarce, Cristian,Sola, Eduardo,Peris, Gabriel,Bayon, J. Carles
, p. 5419 - 5426 (2008/09/17)
The methoxycarbonylation of alkenes catalyzed by palladium(ii) complexes with P,N-donor ligands, 2-(diphenylphosphinoamino)pyridine (Ph 2PNHpy), 2-[(diphenylphosphino)methyl]pyridine (Ph 2PCH2py), and 2-(diphenylphosphino)quinoline (Ph 2Pqn) has been investigated. The results show that the complex [PdCl(PPh3)(Ph2PNHpy)]Cl or an equimolar mixture of [PdCl2(Ph2PNHpy)] and PPh3, in the presence of p-toluensulfonic acid (TsOH), is an efficient catalyst for this reaction. This catalytic system promotes the conversion of styrene into methyl 2-phenylpropanoate and methyl 3-phenylpropanoate with nearly complete chemoselectivity, 98% regioselectivity in the branched isomer, and high turnover frequency, even at alkene/Pd molar ratios of 1000. Best results were obtained in toluene-MeOH (3: 1) solvent. The Pd/Ph2PNHpy catalyst is also efficient in the methoxycarbonylation of cyclohexene and 1-hexene, although with lower rates than with styrene. Related palladium complexes [PdCl(PPh 3)L]Cl (L = Ph2PCH2py and Ph2Pqn) show lower activity in the methoxycarbonylation of styrene than that of the 2-(diphenylphosphinoamino)pyridine ligand. Replacement of the last ligand by (diphenylphosphino)phenylamine (Ph2PNHPh) or 2- (diphenylphosphinoaminomethyl)pyridine (Ph2PNMepy) also reduces significantly the activity of the catalyst, indicating that both the presence of the pyridine fragment as well as the NH group, are required to achieve a high performing catalyst. Isotopic labeling experiments using MeOD are consistent with a hydride mechanism for the [PdCl(PPh3)(Ph2PNHpy)]Cl catalyst. The Royal Society of Chemistry.
