Tag: M.W:100-200

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Synthesis of Cr(III) Salen Complexes as Supramolecular Catalytic Systems for Ring-Opening Reactions of Epoxides

The synthesis of two conformationally restricted Cr(III) salen complexes, 2 and 3, is described. Together, they constitute a supramolecular hydrogen-bonding catalytic system for the recently reported asymmetric ring-opening reactions of epoxides by a dynamic supramolecular catalyst. The synthesis involves state-of-the art transformations in frontline synthetic chemistry applied to heterocyclic chemistry. Hence, palladium-catalyzed reactions were employed, including carbonylative annelation and Suzuki cross-coupling reactions, for the formation of one of the heterocyclic rings (quinolone) and the functionalization of the formed rings. For the construction of the second heterocyclic ring (isoquinolone), a Curtius rearrangement was employed. The corresponding salen ligands were then prepared by Schiff-base reactions, yielding the final complexes after metal insertion. For reference purposes the less conformationally restricted Cr(III) complexes 4 and 5 were also synthesized.

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Stabilized Ru[(H2O)6]3+ in Confined Spaces (MOFs and Zeolites) Catalyzes the Imination of Primary Alcohols under Atmospheric Conditions with Wide Scope

Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type zeolites (Y and X) or a metal organic framework (MOF), to give a reusable heterogeneous catalyst which provides an industrially viable process well below the flammability limit of alcohols and amines.

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Temperature-induced self-assembly of two kinds Zn(II)-based coordination polymers with luminescence properties for application in sensing and adsorption

Temperature-induced self-assembly of coordination polymers (CPs) is of great importance for structural tunability and is quite necessary for further research on structure-property relationships. Two types of CPs {[Zn(L)(DMF)]¡¤3DMF}n (1) (H2L = 4,4?-(trans-cyclohexane-1,2 diyl)bis(azanediyl)bis(carbonyl)dibenzoic acid, DMF = N,N-dimethylformamide) and {ZnL}n (2) are synthesised by the reaction of Zn(NO3)2¡¤6H2O with H2L at different reaction temperatures. CP 1 with a one-dimensional structure is obtained at room temperature, 35 C and 45 C. CP 2 with a two-dimensional structure is prepared by heating at 75 C. When the temperature is further increased to 85 C, 95 C, 105 C and 120 C, CP 2 could still be obtained. Considering the decomposition of ligands and carbonization of solvents at high temperature, 120 C is chosen as the temperature endpoint in the experiment. Single crystal X-ray diffraction analysis indicates that 1 has a chain structure formed by binuclear metal clusters and a bridged carboxylate group. It also indicates that 2 shows a layered structure formed through intermolecular interactions between two adjacent chain motifs. The luminescence properties of 1 and 2 are explored at room temperature in the solid-state. The luminescence intensities of 1 and 2 are weak due to the N-H vibration of the ligand. In order to improve their luminescence properties, we attempt to introduce lanthanide(iii) ions into their channels. Only 2 can accept lanthanide ions Eu3+ and Tb3+ and still maintain its framework, as confirmed by PXRD. Besides, 2 can also sensitize them well. Therefore, the luminescence properties of 2 are improved vastly. The doped material can emit bright red and green light of Eu3+ and Tb3+. A series of EuxTb(1-x)@ZnL coordination polymers are prepared using a post-synthesis method to realize white light emission. The luminescent material Tb3+@ZnL shows a highly sensitive quenching effect to acetone among common solvents. The characteristic emission of Tb3+ could be quenched in the presence of 8 vol% acetone. In addition, 2 could selectively adsorb methylene blue (MB) due to its porosity and can act as a green adsorbent. Compared to 1, 2 is a promising multifunctional material for applications in photoluminescence, luminescent detection and dye adsorption.

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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn¡¯t involve a screen. 21436-03-3, C6H14N2. A document type is Article, introducing its new discovery., Recommanded Product: (1S,2S)-Cyclohexane-1,2-diamine

Chiral Co(III)-salen complex supported over highly ordered functionalized mesoporous silica for enantioselective aminolysis of racemic epoxides

Here we demonstrate the synthesis of a novel chiral Co(iii)-salen complex supported functionalized 2D-hexagonal mesoporous silica material Co(iii)@AFS-1. This material has shown excellent catalytic activity for the regio- and enantioselective asymmetric ring opening (ARO) of terminal and meso epoxides using various aromatic as well as cyclic amines to produce chiral beta-amino alcohols having very good enantioselectivities (ee > 99%) at ambient temperature under solvent-free neat conditions.

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Synthesis of porous organic cage CC3 via solvent modulated evaporation

We demonstrate a Humidity Modulated Solvent Evaporation (HMSE) approach to promote the nucleation and growth of CC3 crystals. This approach relies on the gradual evaporation of dichloromethane (solvent) from a diluted concentration of CC3 precursors deposited on aluminum foil. The slow solvent evaporation allowed enough time for the organization and formation of CC3 porous organic cage. The solvent diffusion rate was modulated by the relative humidity in the system. The slow kinetics implied during the development of CC3 phase, allowed the formation of CC3 crystals. HRTEM, SAED, SEM, and XRD patterns were used as pivotal characterization techniques to follow and confirm the formation of CC3 crystals.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.1436-59-5, Name is cis-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 1436-59-5, name: cis-Cyclohexane-1,2-diamine

Hydrolysis of the amide bond in N-acetylated l-methionylglycine catalyzed by various platinum(II) complexes under physiologically relevant conditions

The hydrolytic reactions between various Pt(II) complexes of the type [Pt(L)Cl2] and [Pt(L)(CBDCA-O,O?] (L is ethylenediamine, en; (¡À)-trans-1,2-diaminocyclohexane, dach; (¡À)-1,2-propylenediamine, 1,2-pn and CBDCA is the 1,1-cyclobutanedicarboxylic anion) and the N-acetylated l-methionylglycine dipeptide (MeCOMet-Gly) were studied by 1H NMR spectroscopy. All reactions were realized at 37 C with equimolar amounts of the Pt(II) complex and the dipeptide at pH 7.40 in 50 mM phosphate buffer in D2O. Under these experimental conditions, a very slow cleavage of the Met-Gly amide bond was observed and this hydrolytic reaction proceeds through the intermediate [Pt(L)(H2O)(MeCOMet-Gly-S)]+ complex. In general, it can be concluded that faster hydrolytic cleavage of the MeCOMet-Gly dipeptide was observed in the reaction with the chloride complex than with corresponding CBDCA Pt(II) complexes. The steric effects of the Pt(II) complex on the hydrolytic cleavage of the amide bond in the MeCOMet-Gly dipeptide were also investigated by 1H NMR spectroscopy. It was found that the rate of hydrolysis decreases as the steric bulk of the CBDCA and chlorido Pt(II) complexes increase (en > 1,2-pn > dach). These results contribute to a better understanding of the toxic side effects of Pt(II) antitumor drugs and should be taken into consideration when designing new potential Pt(II) antitumor drugs with preferably low toxic side effects.

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One-Pot Synthesis of New Organometallic Compounds with Platinum-Carbon Bond

Organometallic compounds of platinum containing ortho metalated para-nitro-benzamidate or 1-naphthalene-methylamine have been prepared by one-pot synthesis. The para-nitro-benzamidate [Pt{K2C,N-pNO2-C6H4C(O)NH}(R,R-DACH)] (compound 2) was obtained starting from [PtCl2(R,R-DACH)] and para-nitro-benzonitrile, which, in the reaction conditions, hydrolyzes to the corresponding amide and forms the dinuclear intermediate [Pt2{mu-N,O-pNO2-C6H4C(O)NH}2(R,R-DACH)2]SO4 (compound 1¡¤SO4) with HH or HT arrangement of the two bridging amidato ligands. Compound 1¡¤SO4, kept at 90 C for few hours, transforms into 2. The ortho-metalated PtII derivative with 1-naphthalene-methylamine [PtCl{K2C,N-C10H6CH2NH2}(DMSO)] (3) was obtained by direct reaction of [PtCl2(DMSO)2] with the amine. Unlike compound 2 that has no labile ligands, compound 3 has Cl and DMSO ligands that can be released, allowing the formation of cross-links with DNA. Oxidation of 3 to the PtIV counterpart was performed with PhICl2 (compound 4). Unexpectedly, although six-coordinate complexes of PtIV are considered to be inert, 4 underwent spontaneous isomerization from the mer to the fac isomer. All compounds have been fully characterized by multinuclear NMR spectroscopy, which has enabled complete assignment of all proton resonances. In the case of compound 2, a single-crystal X-ray investigation was also performed, showing, with the only exception of the puckered cyclohexane ring, a complete planarity of the complex frame, which could favor an intercalative interaction with DNA.

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Application of 1436-59-5. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 1436-59-5, Name is cis-Cyclohexane-1,2-diamine

Rare earth metal complexes based on beta-diketiminato and novel linked bis(beta-diketiminato) ligands: Synthesis, structural characterization and catalytic application in epoxide/CO2-copolymerization

Mesityl substituted beta-diketiminato lanthanum and yttrium complexes [(BDI)Ln{N(SiRMe2)}2] (BDI = ArNC(Me)CHC(Me)NAr, Ar = 2,4,6-Me3C6H2, Ln = La, R = Me (1), H (2a); Ln = Y, R = H (2b)) can be prepared via facile amine elimination starting from [La{N(SiMe3)2}3] and [Ln{N(SiHMe 2)2}3(THF)2] (Ln = Y, La), respectively. The X-ray crystal structure analysis of 1 revealed a distorted tetrahedral geometry around lanthanum with a eta2-bound beta-diketiminato ligand. A series of novel ethylene- and cyclohexyl-linked bis(beta-diketiminato) ligands [C2H4(BDI Ar)2]H2 and [Cy(BDIAr) 2]H2 [Ar = Mes (=2,4,6-Me3C6H 2), DEP (=2,6-Et2C6H3), DIPP (=2,6-i-Pr2C6H3)] were synthesized in a two step condensation procedure. The corresponding bis(beta-diketiminato) yttrium and lanthanum complexes were obtained via amine elimination. The X-ray crystal structure analysis of the ethylene-bridged bis(beta-diketiminato) complex [{C2H4(BDIMes)2}YN(SiMe 3)2] (3b) and cyclohexyl-bridged complexes [{Cy(BDI Mes)2}LaN(SiHMe2)2] (7) and [{Cy(BDIDEP)2}LaN(SiMe3)2] (8) revealed a distorted square pyramidal coordination geometry around the rare earth metal, in which the amido ligand occupies the apical position and the two linked beta-diketiminato moieties form the basis. The geometry of the bis(beta-diketiminato) ligands depends significantly on the linker unit. While complexes with an ethylene-linked ligand adopt a cisoid arrangement of the two aromatic substituents, complexes with cyclohexyl linker adopt a transoid arrangement. Either one (3b) or both (7, 8) of the beta-diketiminato moieties are tilted out of the eta2 coordination mode, resulting in close Ln?C contacts. The beta-diketiminato and linked bis(beta- diketiminato) complexes were moderately active in the copolymerization of cyclohexene oxide with CO2. A maximum of 92% carbonate linkages were obtained using the ethylene-bridged bis(beta-diketiminato) complex [{C 2H4(BDIMes)2}LaN(SiHMe 2)2] (4).

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21436-03-3, Name is (1S,2S)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2, belongs to chiral-catalyst compound, is a common compound. In a patnet, once mentioned the new application about 21436-03-3, Recommanded Product: 21436-03-3

Kinetics and mechanism of water substitution at half-sandwich iridium (III) aqua cations Cp*Ir(A-B)(H2O)2+/+ in aqueous solution (Cp* = eta5-pentamethylcyclopentadienyl anion; A-B = Bidentate N,N or N,O ligand)

The perchlorate complexes of a series of half-sandwich monoaqua cations Cp*Ir(A-B)(H2O)2+/+ with A-B = prol (D/L-proline anion), picac (picoIinic acid anion), R,R-dach [(-)-(1R,2R)-1,2-diaminocyclohexane], R,R-dpen [(+)-(1R,2R)-1,2-diphenylethylenediamine], phen (o-phenanthroIine), and bpy (2,2?-bipyridine) (Cp* = eta5-pentamethylcyclopentadienyl anion) have been prepared and characterized. An X-ray structure analysis of Cp*Ir(R,R-dach)(H2O)(ClO4)2¡¤H 2O has revealed that the cation Cp*Ir(R,R-dach)(H2O)2+ has a distorted pseudo-octahedral coordination geometry. In the case of A-B = prol, crystallization from water led to the trinuclear complex [Cp*Ir(D-prol)]3(ClO4)3, which has also been characterized by X-ray structure analysis. The experimental data suggest that in aqueous solution the trinuclear proline complex dissociates to form the cation Cp*Ir(D-prol)(H2O)+. The proton dissociation constants of the coordinated water in Cp* Ir(A-B)(H2O)2+/+ have been determined as pKa = 7.5 (A-B = bpy) and pKa = 7.1 (A-B = R,R-dach and picac). Substitution of the water in Cp*Ir(A-B)(H2O)2+/+ by the monodentate ligands L = py (pyridine), DMS (dimethyl sulfide), TU (thiourea), and monodentate anions according to the Equation Cp*Ir(A-B)(H2O)2+/+ + L ? Cp*Ir(A-B)L2+/+ + H2O has been studied by multi-wavelength stopped-flow spectrophotometry in aqueous solution at I = 0.2 M. This kinetic investigation, carried out at different concentrations, temperatures, and pressures, showed that the process obeys second-order kinetics, where rate = kL[Cp*Ir(A-B)H2O2+/+][L]. The magnitude of the second-order rate constant kL depends on the nature of both A-B and L. The data for kL have been found to range from 6.4 ¡Á 104 M-1S-1 (A-B = D-prol; L = TU) to 10.5 M-1S-1 (A-B = bpy; L = py) at 298 K. The activation parameters for water substitution at Cp*Ir(A-B)(H2O)2+/+ (A-B = bpy, R,R-dach, and picac) by L = TU have been evaluated. The activation volumes of DeltaV? = +2.3, +7.4, and +7.3 cm3 mol-1, respectively, are supportive of an Id mechanism. The results regarding the kinetic lability of the coordinated water in the monoaqua cations Cp*Ir(A-B)(H2O)2+/+ are compared to those obtained for the triaqua cation Cp*Ir(H2O)32+.

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 21436-03-3, Name is (1S,2S)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 21436-03-3, Quality Control of: (1S,2S)-Cyclohexane-1,2-diamine

New chiral thiophene-salen chromium complexes for the asymmetric Henry reaction

Chiral thiophene-salen chromium complexes were investigated in their monomeric form as soluble catalysts in the enantioselective Henry reaction of several aldehydes. The anodic polymerization of one complex led to an insoluble powder that was successfully used as a heterogeneous catalyst for the transformation of 2-methoxybenzaldehyde with enantiomeric excesses up to 77%. The polymerized catalyst was recovered and also recycled in an original multisubstrate procedure

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