Tag: M.W:200-300

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Characterization of a rhodium-sparteine complex, [((-)-sparteine) Rh(eta4-COD)]+: Crystal structure and DNMR/DFT studies on ligand-rotation dynamics

A cationic rhodium-sparteine complex, [((-)-sparteine)Rh(eta4- COD)]+ (1+; COD = 1,5-cyclooctadiene) was obtained, isolated as its tetrafluoroborate salt (1BF4), and characterized using X-ray crystallography and multinuclear (1H, 13C) NMR spectroscopy. This is the first structurally characterized sparteine complex of rhodium. The Rh-N bonds are unusually long (2.214(3) and 2.242(3) A), apparently due to steric repulsion between COD and sparteine. 1H NMR exchange experiments (EXSY) demonstrate a dynamic process that results in an overall 180 rotation of the COD methine protons in solution (CD 2Cl2) with a first-order rate constant of 460 s -1 at the coalescence temperature (314 K) and interpolated rate constant of 150 s-1 at 298 K. Temperature-dependent NMR studies yield DeltaH? = 13.0 ¡À 0.3 kcal mol-1, DeltaS? = -5 ¡À 1 cal mol-1 K-1, such that DeltaG?298 = 14.3 ¡À 0.3 kcal mol-1. DFT studies (B3LYP) indicate that the loosely bound (-)-sparteine ligand rotates through a pseudo-tetrahedral transition state where both ligands are rotated approximately 90 relative to each other. While both ligands remain bound (eta4-COD, kappa2-sparteine), bonding to sparteine is weakened much more than bonding to COD in the transition state. DFT computed DeltaG?298 and DeltaS? values (15.55 kcal mol -1 and -2.67 cal mol-1 K-1, respectively) agree very well with the experimental values. Attempts to find alternative mechanisms involving partial dechelation of COD and (-)-sparteine yielded slightly higher barriers along with positive DeltaS values for intermediate formation.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Chemistry is traditionally divided into organic and inorganic chemistry. HPLC of Formula: C14H19FeN, The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent£¬Which mentioned a new discovery about 31886-57-4

Thermal ring-opening polymerization of planar-chiral Sila[1]ferrocenophanes

The new Me2Si-bridged [1]ferrocenophane ([1]FCP) with one iPr group in alpha position on a Cp ring was synthesized in an enantiopure (Sp-4) and a racemic form (rac-4). The molecular structure of rac-4 was determined by single-crystal X-ray analysis (tilt angle alpha = 20.15(14)). Experimental and calculated molecular structures of the related [1]FCPs with one (Sp-4 and rac-4) or two iPr groups (Sp,Sp-4) are compared to that of the nonsubstituted [1]FCP Me2Sifc. Differential scanning calorimetry (DSC) measurements resulted in HROP of 72(¡À2) kJ mol-1 for rac-4 and 62(¡À2) kJ mol-1 for the known Sp,Sp-4. While thermal ring-opening polymerization of Sp,Sp-4 gave insoluble material, the monosubstituted monomers Sp-4 and rac-4 resulted in soluble polymers with molecular weights (Mw) of 5.3 ¡Á 106 and 2.6 ¡Á 106 Da, respectively. Investigation of the polymer structures by 29Si NMR spectroscopy gave further evidence that the breakage of Si-Cp bonds occurs in the thermal ROP process of sila[1]ferrocenophanes.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, Application In Synthesis of (S)-N,N-Dimethyl-1-ferrocenylethylamine, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 31886-57-4, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, molecular formula is C14H19FeN

Molecular structures of Ugi’s amine ferrocene-conjugates with R,R-tartaric acid and DFT calculations versus experimental resolution of their diastereomers

Classical synthetic approach to highly enantiomeric-enriched ferrocenes relies on the formation of their conjugates with (R,R)-tartaric acid. Herein, the quantum chemical calculations based on X-ray data as an initial approximation, were carried out for both (R)- and (S)-diastereomers of N,N-(dimethyl-1-ferrocenyl)ethylamine (Ugi’s amine) with (R,R)-tartaric acid. A high correlation between the experimental data and the calculated Gibbs free energies values of solvation was obtained. Based on the advanced DFT calculations, the chemical aspects of the separation of the diastereomeric complexes of (R)- and (S)-FcCH(CH3)N(CH3)2 with (R,R)-tartaric acid were clarified. Quantum chemical calculations made it possible to justify the use of methanol as a solvent in the successful separation of the diastereomeric complexes of the Ugi’s amine. This mathematical approach can be used in practice to separate racemates of other bioactive ferrocene compounds, for example, ferrocenyl alkyl azoles.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

31886-57-4, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, belongs to chiral-nitrogen-ligands compound, is a common compound. SDS of cas: 31886-57-4In an article, once mentioned the new application about 31886-57-4.

Optically Active Transition-Metal Complexes. 9.1 A General Stereoselective Route to alpha-Chiral (A)-Tricarbonyl(eta6-ethylbenzene)chromium Complexes. Novel Organometallic Phosphine Catalysts for the Asymmetric Hydrovinylation Reaction

Treatment of (R)-[{alpha-(dimethylamino)ethyl}-eta6-benzene]Cr(CO)3 with esters of chloroformic acid leads to stereoselective substitution of the dimethylamino group for a chloro substituent. The reaction can be extended to systems in which the chromium arene complex, after metalation, is diastereoselectively substituted in the ortho position with carbon and silicon electrophiles to generate planar chirality. The chloro group in turn can be replaced stereoselectively for various phosphorus, nitrogen, and oxygen nucleophiles. Both substitution reactions in the benzylic position proceed via retention of configuration. The addition of cyanide is not stereospecific. The phosphine derivatives are efficient catalysts for the enantioselective hydrovinylation of styrene to 3-phenyl-1-butene. X-ray crystal structures establish the absolute configuration of (R)-[(alpha-chloroethyl)eta6-benzene]Cr(CO)3, (R)-[{alpha-(diphenylphosphanyl)ethyl}-alpha6-benzene]Cr(CO) 3, and (pS,S)-[l-(alpha-cyanoethyl)-2-methyl-eta6-benzene]Cr(CO) 3.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments. Recommanded Product: 492-08-0. Introducing a new discovery about 492-08-0, Name is (+)-Sparteine

Profiling of a prescription drug library for potential renal drug-drug interactions mediated by the organic cation transporter 2

Drug-drug interactions (DDIs) are major causes of serious adverse drug reactions. Most DDIs have a pharmacokinetic basis in which one drug reduces the elimination of a second drug, leading to potentially toxic drug levels. As a major organ of drug elimination, the kidney represents an important site for DDIs. Here, we screened a prescription drug library against the renal organic cation transporter OCT2/SLC22A2, which mediates the first step in the renal secretion of many cationic drugs. Of the 910 compounds screened, 244 inhibited OCT2. Computational analyses revealed key properties of inhibitors versus noninhibitors, which included overall molecular charge. Four of six potential clinical inhibitors were transporter-selective in follow-up screens against additional transporters: OCT1/SLC22A1, MATE1/SLC47A1, and MATE2-K/SLC47A2. Two compounds showed different kinetics of interaction with the common polymorphism OCT2-A270S, suggesting a role of genetics in modulating renal DDIs.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, Computed Properties of C14H19FeN, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 31886-57-4, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, molecular formula is C14H19FeN

Insight into the Thermal Ring-Opening Polymerization of Phospha[1]ferrocenophanes

A mixture of cis/trans isomers of phospha[1]ferrocenophanes equipped with one iPr group at the alpha position to the bridging PhP moiety was prepared. Both isomers (cis-4 and trans-4) were obtained as racemates and could be separated so that their thermal properties were investigated individually. The molecular structure of cis-4 was determined by single-crystal X-ray analysis showing a tilt angle alpha=26.35(8). Interconversion between both isomers occurred in the melt at elevated temperatures and revealed that the trans isomer is thermodynamically more stable. Structural and thermodynamic data was complemented by DFT calculations (B3PW91/6-311+G(d,p) and B3PW91-D3(BJ)/6-311+G(d,p)). Performance of thermal ring-opening polymerization (ROP) of trans-4 at 230 C gave polymers and cyclic oligomers. Gel permeation chromatography (GPC) of the sulfurized polymer resulted in a molecular weight of 62.5 kDa (Mw) and a polydispersity index of 1.39 (PDI). Mass spectrometric analysis of the oligomers showed the presence of cyclic species from dimers to heptamers. After sulfurization, preparative thin layer chromatography led to the separation of three isomeric dimers. Structural characterization of these dimers by single-crystal X-ray analysis led to the conclusion that the Fe?Cp bond breaks during the thermal ROP process. A mechanism similar to the known mechanism of the photolytic ROP of ferrocenophanes is proposed.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Computed Properties of C14H19FeN, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 31886-57-4, in my other articles.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Reference of 492-08-0, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.492-08-0, Name is (+)-Sparteine, molecular formula is C15H26N2. In a Article£¬once mentioned of 492-08-0

Nematicidal Activity of Matrine and Its Derivatives against Pine Wood Nematodes

The nematicidal activity of matrine and its derivatives isolated from the epigeal part of Sophora flavescens was examined against the pine wood nematode (Bursaphelenchus xylophilus). The nematicidal activity of matrine, which is one of the major alkaloids in the root of the plant, was poor. However, sophocarpine, one of the unsaturated derivatives of matrine, had strong nematicidal activity against another unsaturated derivative, sophoramine, had such activity, but it was less than that nematodes; another unsaturated derivative, sophoramine, had such activity, but it was less than that of sophocarpine. These results suggest that the degree of unsaturation in the 6-lactam ring of matrine type alkaloids is important to nematicidal activity.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, SDS of cas: 31886-57-4, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 31886-57-4, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, molecular formula is C14H19FeN

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality

Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Electric Literature of 31886-57-4, 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. 31886-57-4, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, molecular formula is C14H19FeN. In a Patent£¬once mentioned of 31886-57-4

PROCESS FOR THE SYNTHESIS OF ARYL HYDRAZINES

The invention relates to a process for the synthesis of aryl hydrazinesof formula I or a salt thereof, which process comprises subjecting an arene of formula II to a coupling reaction with hydrazine or a derivative thereof, wherein the coupling reaction is conducted in the presence of a catalyst comprising palladium and a diphosphine ligand, wherein the phosphorus atoms are connected through two, three, four, or five atoms selected from car- bon, nitrogen, oxygen or iron, and in which the non-connecting phosphorus substituents are C1- C 10-alkyl or C3-C10-cycloalkyl, wherein the amount of Pd used is up to 0.5 mol-% relative to the amount of arene of formula II; and a base.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Application In Synthesis of (S)-N,N-Dimethyl-1-ferrocenylethylamine, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 31886-57-4, name is (S)-N,N-Dimethyl-1-ferrocenylethylamine. In an article£¬Which mentioned a new discovery about 31886-57-4

Synthesis and electrochemical properties of mono- And (¡À)-l,2-dia!kylferrocenes and alkylferrocenium hexafluorophosphates in aqueous and micellar media

Simple methods have been developed for the preparation of a series of n-alkylferrocenes H(CH2)Fc (n = 3, 5-8, or 12) based on Friedel-Crafts acylation of ferrocenes followed by reduction of the corresponding ketones with Zn amalgam. The properties of H(CH2>nFc and the corresponding ferrocenium ions in micellar aqueous solutions and the behavior of watersoluble cations H(CH2)nFc+ in the absence of micelles were studied by cyclic voltammetry. In all cases, the formal redox potentials of ferrocenes (? ‘) increase linearly as n increases up to 8. Whether micelles are present or not, the corresponding correlation equation has the following form: ?”‘= a + pn, where beta= 29 mV in all cases. The synthesis of (¡À)-l-ethyI-2methylferrocene from racemic a-dimethylaminoethylferrocene is reported.

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Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis