- Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH
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This study describes the electrocatalytic, anticancer, and density functional theory (DFT) studies of a nickel complex, [NiCl(P^N^P)]Cl.EtOH, based on a neutral P^N^P-type pincer ligand (P^N^P = bis[(2-diphenylphosphino)ethyl]amine). The ligand was synthesized without time-consuming and costly amine protection. It was characterized by 1H NMR, 31P NMR, Fourier transform infrared (FT-IR), UV–vis, and single-crystal X-ray diffraction. The complex was isolated as a solvated chloride salt and characterized by FT-IR, UV–visible, 1H NMR, 13C NMR, and 31P NMR spectroscopies as well as single-crystal X-ray diffraction and CHN analysis. The ligand and complex crystallized in a monoclinic P21/c space group. The molecular structure of the complex contains a four-coordinated distorted nickel ion with square-planar geometry. The electrocatalytic hydrogen ion reduction was studied for the nickel complex in an acidic non-aqueous medium. Cyclic voltammetry studies showed that this complex is an efficient electrocatalyst for hydrogen evolution at the potential of the Ni(II/I) couple. As a potential anticancer agent, the biological activities of the Ni complex were tested against two human cancer cell lines (MCF7 and HT29). The IC50 results demonstrated that the nickel complex has better cytotoxic activity than cis-platin against the human breast cancer cell (MCF7) line. DFT calculations were performed to study the kinetics and thermodynamics of the pincer ligand's synthetic procedure and its Ni complex. Time-dependent DFT calculations were performed to calculate the pincer ligand's UV–vis spectra and the complex, which was in agreement with the experimental data. To assign the calculated UV spectra, molecular orbital calculations were performed. Finally, a modified mechanism was proposed for the electrocatalytic hydrogen ion reduction by [Ni(P^N^P)Cl]Cl.EtOH. The theoretical calculations showed that the cycle is thermodynamically favorable.
- Mohammadnezhad, Gholamhossein,Abad, Saeed,Farrokhpour, Hossein,G?rls, Helmar,Plass, Winfried
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- Ruthenium-catalyzed ester reductions applied to pharmaceutical intermediates
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Ruthenium pincer complexes were synthesized and used for catalytic ester reductions under mild conditions (～5 bar of hydrogen). An experimental design approach was used to optimize the conditions for yield, purity, and robustness. Evidence for the catalytically active ruthenium dihydride species is presented. Observed intermediates and side products, as well as time-course data, were used to build mechanistic insight. The optimized procedure was further demonstrated through scaled-up reductions of two pharmaceutically relevant esters, both in batch and continuous flow.
- Shaalan, Youssef,Boulton, Lee,Jamieson, Craig
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supporting information
p. 2745 - 2751
(2020/11/30)
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- Sustainable Manganese-Catalyzed Solvent-Free Synthesis of Pyrroles from 1,4-Diols and Primary Amines
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A general and selective metal-catalyzed conversion of biomass-derived primary diols and amines to the highly valuable 2,5-unsubstituted pyrroles has been developed. The reaction is catalyzed by a stable nonprecious manganese complex (1 mol %) in the absence of organic solvents whereby water and molecular hydrogen are the only side products. The manganese catalyst shows unprecedented selectivity, avoiding the formation of pyrrolidines, cyclic imides, and lactones.
- Borghs, Jannik C.,Lebedev, Yury,Rueping, Magnus,El-Sepelgy, Osama
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supporting information
p. 70 - 74
(2019/01/11)
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- TRANSITION METAL ISONITRILE CATALYSTS
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The present disclosure relates to new transition metal isonitrile compounds, processes for the production of the compounds and the use of the compounds as catalysts. The disclosure also relates to the use of the metal isonitrile compounds as catalysts for hydrogenation and transfer hydrogenation of compounds containing one or more carbon-oxygen, and/or carbon-nitrogen and/or carbon-carbon double bonds.
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Page/Page column 21
(2018/11/22)
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- Stereospecific polymerization of 1,3-butadiene catalyzed by cobalt complexes bearing N-containing diphosphine PNP ligands
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A series of cobalt complexes bearing N-containing diphosphine PNP ligands has been synthesized and characterized. The nature of the ligand structure affects the binding of the ligand to the cobalt center and determines the coordination geometry of the cobalt complexes. All the complexes have been employed to catalyze the polymerization of 1,3-butadiene, in combination with methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC) as the cocatalyst. Both the nature of the ligand and the type of cocatalyst had a remarkable influence on the polymerization activity, microstructure and molecular weight of the resulting polymers. The [Co]/MAO catalytic systems resulted in relatively lower conversions of butadiene and cis-1,4 contents in the polymers than the corresponding [Co]/EASC catalytic systems. Upon activation with EASC, the polymerization behaviors of the catalytic systems were also affected by the reaction parameters.
- Chen, Lin,Ai, Pengfei,Gu, Jianming,Jie, Suyun,Li, Bo-Geng
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- Asymmetric hydrogenation with antibody-achiral rhodium complex
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An asymmetric hydrogenation of an amino acid precursor was catalyzed by the rhodium cyclooctadiene phosphine complex of a transition metal with immunoglobin. The hapten was covalently attached to a limpet hemocyanin (KLH) or bovine serum albumin (BSA) through activation of the carboxyl group in the hapten molecule using carbonyldiimidazole. The conjugates KLH-1 and BSA-1 were purified by size exclusion chromatography and used as an antigen to immunize mice and in enzyme linked immunosorbent assay (ELISA). The Rh complex was added to the aqueous solution of the monoclonal antibody under argon atmosphere at room temperature. It was found that the antibody IG8 could bind substrate than the hapten molecules, and the antibody IG8-Rh complex is stereoselective catalyst with substrate specificity through second sphere coordination.
- Yamaguchi, Hiroyasu,Hirano, Tohko,Kiminami, Hideaki,Taura, Daisuke,Harada, Akira
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p. 3571 - 3573
(2008/10/09)
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- Reactivity of a cationic square-planar palladium(II) chloro complex containing bis[2-(diphenylphosphino)ethyl]amine: Chloro substitutions by anionic ligands and formation of neutral digold(I) compounds possessing linear PAuX fragments. The x-ray crystal structure of Au2[Ph2P(CH2)2N(NO) (CH2)2PPh2]Cl2
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The interaction of sodium tetrachloropalladate(II) with the potentially tridentate aminophosphine bis[2-(diphenylphosphino)ethyl]amine (PNHP) in 1:1 molar ratio leads to the formation of the four-coordinate complex [Pd(PNHP)Cl]Cl (1). Complex 1 undergoes chloro substitution reactions with NaX (X = Br, I), CuCl, AgNO3, the amino acid N-acetyl-L-cysteine (AcCysSH) and the tripeptide reduced glutathione (γ-L-Glu-L-Cys-Gly, GSH) affording [Pd(PNHP)X]X′ [X = X′ = Br (2), I (3), NO3 (4); X = Cl, X′ = CuCl2 (1a); X′ = Cl, X = RS = AcCysS (8), GS (9)]. However, gold(I) induces abstraction of the aminophosphine from the ionic complexes 1 and 2 to produce the neutral compounds Au2(PNHP)X2 [X = Cl (5), Br (6)]. The dinuclear complex Au2(PN(NO)P)Cl2 (5a), containing the ligand bis[2-(diphenylphosphino)ethyl]nitrosylamine, was formed by reaction of 4 with gold(I) in the presence of traces of nitrosyl chloride. Addition of one molar equivalent of PNHP to 1 results, by a ring-opening process, in the formation of [Pd(PNHP)2]Cl2 (7) in which the palladium is five-coordinate. The ionic complexes 1, 2 and 4 were shown by X-ray diffraction to be distorted square-planar and complex 2 has a N-H...Br bond of 2.371 A with the ligand adopting a boat conformation. The X-ray crystal structure of the novel neutral compound 5a shows linear P-Au-Cl arrangements with intermolecular Au...Au interactions of 3.0412(9) A.
- Garcia-Seijo, M. Ines,Habtemariam, Abraha,Parsons, Simon,Gould,Garcia-Fernandez, M. Esther
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p. 636 - 644
(2007/10/03)
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- Synthesis of Functional Chelating Diphosphines Containing the Bisamino Moiety and the Use of These Materials in the Preparation of Water-Soluble Diphosphine Complexes of Transition Metals
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Acylation of bisamine provides a flexible synthesis of functionalized chelating diphosphines.This reaction offers a route to diphosphine complexes of transition metals having a wide range of structures and physical properties and especially to water-soluble complexes.The aqueous solubility of the free ligands and of the complexes prepared from them depend on the ligand, on the metal, and on other materials (especially surfactants) present in the solution.We describe typical preparations of ligands and outline the properties of their complexes with certain transition metals.
- Nuzzo, Ralph G.,Haynie, Sharon L.,Wilson, Michael E.,Whitesides, George M.
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p. 2861 - 2867
(2007/10/02)
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