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Protonolysis and Amide Exchange Reactions of a Three-Coordinate Cobalt Amide Complex Supported by an N-Heterocyclic Carbene Ligand

A three-coordinate cobalt species, IPrCoCl{N-(SiMe3)2} [1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene], was synthesized by the reaction of {IPrCoCl2}2 with NaN(SiMe3)2. Compound 1 is a useful starting material for low-coordinate (IPr)Co species. 1 reacts with 2,6-di-tert-butyl-4-methylphenol (BHT-H) via aminolysis of the Co-N bond to generate a three-coordinate phenoxide complex, IPrCoCl(O-2,6-tBu2-4-MeC6H2) (2). The reaction of 1 with 2,6-diisopropylaniline (NH2DIPP) generates IPrCoCl(NHDIPP) (4), which undergoes disproportionation to form a mixture of 4, {IPrCoCl2}2, and IPrCo(NHDIPP)2 (3). The same product mixture is formed by the reaction of 1 with Li[NH(DIPP)], which unexpectedly proceeds by amide exchange. Compound 3 was synthesized independently by the reaction of {IPrCoCl2}2 with 4 equiv of Li[NH(DIPP)]. The reaction of 1 with the bulkier lithium 2,6-dimesitylanilide (LiNHDMP) also proceeds by amide exchange to generate IPrCoCl(NHDMP) (5), which is stable toward disproportionation. Compounds 1 and 2 exhibit trigonal-planar geometries at cobalt in the solid state. The solid-state structure of 3 also contains a trigonal-planar cobalt center and exhibits close Co—H contacts involving the methine hydrogen atoms of the NH(DIPP) groups in the axial positions. The solid-state structure of 5 features an interaction between cobalt and a flanking aryl group of the anilide ligand, resulting in pyramidalization of the cobalt center. (Chemical Equation Presented).

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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. 14098-44-3, Name is Benzo-15-crown-5, molecular formula is C14H20O5. In a Article£¬once mentioned of 14098-44-3, SDS of cas: 14098-44-3

Synthesis and structural characterization of a new supermolecular compound: H3PW12O40¡¤6C14H20O5¡¤16H2O (C14H20O5 = benzo-15-crown-5)

The new supermolecular compound, H3PW12O40¡¤6C40H20O5¡¤16H2O (C14H20O5 = benzo-15-Crown-5), was synthesized in methanol solution and structurally characterized by elemental analysis, IR, 1H NMR and single crystal X-Ray diffraction. It was shown that PW12O40/3- anions possess alpha-Keggin structure with crystallographic disorder. The disorder averages the W-W distances and W-O(b/c)-W angles, but the vibrational ellipsoids of oxygen atoms are not elongated obviously. In the compound, water blocks are formed, which are hydrogen-Bonded to crown ether molecules. Since crown ether molecules fetter the movement of water molecules and oxonium ions, the conductivity is lower (rho(r.t.) < 10-7 S cm-1). The compound crystallizes in the triclinic space group PI? with a = 14.154(3), b = 15.598(3), c = 18.023(3) A?, alpha = 67.17(3), beta = 89.83(3), gamma = 83.27(3), V = 3638.1(13) A?3, Z = 1 and R1(wR2) =0.0655(0.1701). (C) 2000 Elsevier Science B.V. Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.SDS of cas: 14098-44-3, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 14098-44-3, in my other articles.

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Final Thoughts on Chemistry for 14187-32-7

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Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na]2 W6O19¡¤DB18C6¡¤H2O 1 and [(DB18C6)(DMF)2Na]4 W10O32¡¤2DMF¡¤2H2O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) A?, beta = 115.15(2), V = 7678(3) A?3, Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) A?, beta = 91.78(2), V = 7528(3) A?3, Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the ‘naked’ polyanions W10O324- via the electrostatic attraction.

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Can You Really Do Chemisty Experiments About 23190-16-1

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Chiroptical Asymmetric Reaction Screening via Multicomponent Self-Assembly

Self-assembly of a stereodynamic phosphine ligand, Pd(II), and a chiral amine, amino alcohol, or amino acid generates characteristic UV and CD signals that can be used for quantitative stereochemical analysis of the bound substrate. A robust mix-and-measure chiroptical sensing protocol has been developed and used to determine the absolute configuration, ee, and yield of an amine produced by Ir-catalyzed asymmetric hydrogenation of an iminium salt. The analysis requires only 1 mg of the crude reaction mixture and minimizes cost, labor, time, and waste.

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Discovery of 250285-32-6

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Estimation of sigma-Donation and pi-Backdonation of Cyclic Alkyl(amino) Carbene-Containing Compounds

Herein, we present a general method for a reliable estimation of the extent of pi-backdonation (CcAAC?E) of the bonded element (E) to the carbene carbon atom and CcAAC?E sigma-donation. The CcAAC?E pi-backdonation has a significant effect on the electronic environments of the 15N nucleus. The estimation of the pi-backdonation has been achieved by recording the chemical shift values of the 15N nuclei via two-dimensional heteronuclear multiple-bond correlation spectroscopy. The chemical shift values of the 15N nuclei of several cAAC-containing compounds and/or complexes were recorded. The 15N nuclear magnetic resonance chemical shift values are in the range from -130 to -315 ppm. When the cAAC forms a coordinate sigma-bond (CcAAC?E), the chemical shift values of the 15N nuclei are around -160 ppm. In case the cAAC is bound to a cationic species, the numerical chemical shift value of the 15N nucleus is downfield-shifted (-130 to -148 ppm). The numerical values of the 15N nuclei fall in the range from -170 to -200 ppm when sigma-donation (CcAAC?E) of cAAC is stronger than CcAAC?E pi-backacceptance. The pi-backacceptance of cAAC is stronger than sigma-donation, when the chemical shift values of the 15N nuclei are observed below -220 ppm. Electron density and charge transfer between CcAAC and E are quantified using natural bonding orbital analysis and charge decomposition analysis techniques. The experimental results have been correlated with the theoretical calculations. They are in good agreement.

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Establishment of an efficient synthetic route to 3,4:3?,4?-bis(3,6,9-trioxaundecane-1,11-dioxy)benzil

3,4:3?,4?-Bis(3,6,9-trioxaundecane-1,11-dioxy)benzil (1) [bis(crown ether)benzil] was prepared by three different routes in which the third route C, including the method of Sonogashira-coupling, was the most efficient method with the overall yield of 50%. Further, the method of synthesizing the novel compound 3,4:3?,4?-bis[3,4-(3,6,9-trioxaundecane-1,11-dioxy)]benzoin (6) [bis(crown ether)benzoin], which has not yet been prepared appropriately, was also provided.

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Archives for Chemistry Experiments of 1436-59-5

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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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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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Archives for Chemistry Experiments of 250285-32-6

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Application of 250285-32-6, An article , which mentions 250285-32-6, molecular formula is C27H37ClN2. The compound – 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride played an important role in people’s production and life.

Synthesis, properties, and reactivity of palladium and nickel NHC complexes supported by combinations of allyl, cyclopentadienyl, and indenyl ligands

The synthesis of a series of Pd and Ni complexes containing combinations of 2-methylallyl (C4H7), cyclopentadienyl (C 5H5, Cp), and indenyl (C7H9, Ind) ligands is reported. In all cases these complexes are supported by the electron-donating N-heterocyclic carbene ligand 1,3-bis(2,6-diisopropylphenyl)- 1,3-dihydro-2H-imidazol-2-ylidene (IPr). The mixed Cp/2-methylallyl complexes (eta1-Cp)(eta3-2-methylallyl)Pd(IPr) ( CpAllPd) and (eta5-Cp)(eta1-2-methylallyl) Ni(IPr) (CpAllNi) were synthesized through the reaction of IPr with (Cp)(2-methylallyl)M (M = Ni, Pd). The binding mode of the ligands is different in the two complexes, and as a result the total valence electron count around the metal is 18 for the Ni complex and only 16 for the Pd species. In the case of Pd, an analogue of CpAllPd containing an indenyl ligand, (eta1-Ind)(eta3-2-methylallyl)Pd(IPr) ( IndAllPd), was synthesized through the reaction of (eta3-Ind)Pd(IPr)Cl (IndClPd) with (2-methylallyl) magnesium chloride. The corresponding Ni complex (eta5-Ind) (eta1-2-methylallyl)Ni(IPr) (IndAllNi) could not be isolated. The binding modes of the ligands in the mixed indenyl/Cp complexes (eta1-Ind)(eta5-Cp)M(IPr) (M = Ni ( IndCpNi), Pd (IndCpPd)) were the same for both Ni and Pd. IndCpPd was prepared through the reaction of IndClPd with NaCp, while IndCpNi was synthesized through the reaction of (eta5-Cp)Ni(IPr)Cl (CpClNi) with lithium indenyl. Similarly, the structures of the bis(Cp) complexes (eta5-Cp) (eta1-Cp)Ni(IPr) (CpCpNi) and (eta5-Cp) (eta1-Cp)Pd(IPr) (CpCpPd) were identical for the two different metals. In contrast to CpCpPd, which is an 18-electron complex, the related bis(indenyl) Pd complex (eta3-Ind) (eta1-Ind)Pd(IPr) (IndIndPd) is a 16-electron species, while no Ni analogue of IndIndPd was characterized. Preliminary reactivity studies with electrophiles indicate that, in all systems with mixed ligands, the eta1-ligand is nucleophilic and reacts selectively. The complexes CpAllPd, CpAllNi, CpCpPd, CpCpNi, IndClPd, IndAllPd, and IndIndPd were characterized by X-ray crystallography.

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New unsymmetrical oxovanadium(IV) complexes of mixed-donor amido and oxo ligands

The novel, unsymmetrical, mixed-donor, tetradentate amido, and oxo complexes of V(IV) of the general formula VOLx were synthesized by a nontemplate method and characterized by physico-chemical methods. The ligands were prepared by a two-stage aldol condensation reaction in the molar ratio 1:1 of 2-hydroxybenzaldehyde, 2?-hydroxyacetophenone, or 2?,4?- dihydroxyacetophenone and 1,2-diaminopropane of the general formula HA x (x = 1-3) as precursors. The tetradentate mixed donor ligands of the general formula H2Lx (x = 1-6) were obtained by condensation reaction of precursors with appropriate ketone or aldehyde. The synthesis of the ligand system, described here, is an efficient and easy method with the advantages of high yield, selectivity, and short reaction times. Only a brown polymeric form was obtained for VOL2 and green monomeric forms were obtained for VOLx, x = 1, 3-5, while in the presence of strong field ligands only monomeric forms were obtained. These observations suggest that monomeric forms of oxovanadium(IV) complexes exhibit a coordination number of five with N2O3 donor sets and the polymeric form exhibits a coordination number of six with N2O4 donor sets. Analytical data, 1H NMR, IR, UV-VIS spectra, and elemental analyses confirm the nature of the products.

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