Improved synthesis of pincer ligand precursor, and synthesis and structural characterization of terphenyl scaffolded S–C–S palladium pincer complex

Schroder, Paul M.; Spilker, Thomas F.; Luu, Wilson; Updegraff, James B.; Kwan, Man Lung Desmond; Challen, Paul R.; Protasiewicz, John D.

doi:10.1016/j.inoche.2009.08.036

Cited by 5 publications

(2 citation statements)

References 35 publications

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“…Pincer-type molecules/ions are an exciting class of ligands that have received increasing attention in modern organometallic chemistry. [1][2][3] Metal complexes of pincer-type ligands have been successfully employed for a wide variety of applications including supramolecular chemistry, [4][5][6] antibacteria, [7] anticancer, [8][9][10][11][12] sensors, [13,14] and of course for catalytic reactions (heterogenic and homogenic). [15][16][17][18][19][20][21][22][23][24] The earliest synthesis of these ligands dates back to 1976 but it wasn't until in 1989 that van Koten applied the term "pincer" word for this group of ligands.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

Mohammadnezhad

Abad

Farrokhpour

et al. 2020

Applied Organom Chemis

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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.

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Section: Introductionmentioning

confidence: 99%

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

Mohammadnezhad

Abad

Farrokhpour

et al. 2020

Applied Organom Chemis

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“…Seven-membered palladacycles are relatively scarce, and, to the best of our knowledge, only one of them has been obtained by metalation of an arene . The synthesis of the reported seven-membered palladacycles comprises (1) insertion of alkynes into the Pd–C bond of five-membered palladacycles or of RNC into the Pd–C bond of six-membered palladacycles, (2) coordination of a donor atom of a functionalized ligand previously C-bonded to Pd(II), (3) coordination to Pd(II) of bis-N-heterocyclic carbenes, bis-ylides, or phosphine-carbene ligands usually generated in situ, (4) oxidative addition of Ar P,N,S X (Ar P,N,S = PR 2 , NR 2 , py, or RS-functionalized aryl; X = Br, I) to Pd(0) compounds, followed occasionally by a C–C coupling reaction, and (5) C–H activation by a Pd(II) salt, where the metalated CH can belong to an allyl, a phenyl, or a methyl group . It is worthy to note that the latter are very uncommon processes: the allylic activation affords a pincer complex, the C aryl –H activation occurs in a tetraphenylcyclobutadiene complex of Co(II), and the C(sp 3 )–H palladation takes place in a di- tert -butyl(biaryl)phosphine coordinated to Pd(II) .…”

Section: Introductionmentioning

confidence: 99%

C–H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas

et al. 2016

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The dimeric cyclometalated complexes [Pd2{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}2(μ-Cl)2] (R = Me (1a), H (1b)) are prepared by reacting 1,1-dimethyl-3-phenylpropylammonium or 1-methyl-3-phenylpropylammonium triflate with Pd(OAc)2 in a 1:1 molar ratio and subsequent treatment with excess NaCl. The mononuclear derivatives [Pd{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}Cl(L)] (L = PPh3, R = Me (3a), H (3b); L = 4-picoline (4-pic), R = Me (4a), H (4b)) were prepared from 1a,b by splitting the chloro bridges with the neutral ligands L. A conformational analysis of the mononuclear palladacycles in solution has been carried out. Insertion of CO takes place into the Pd-C bond of complexes 1a,b, affording Pd(0) and the tetrahydro-benzazepinone 5a or 5b, which possesses potential pharmacological interest. Additionally, the triflate salt A or B undergoes catalytic carbonylation with CO to afford the corresponding N,N'-dialkylurea, using Pd(OAc)2/Cu(OAc)2, in boiling acetonitrile. The crystal structures of 3a·(1)/2H2O, 3b, 4b·CHCl3, and 5a were determined by X-ray diffraction studies.

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Insertion of Symmetric Alkynes into the σ[Pd–C(sp², Ferrocene)] Bond of Palladacycles with [C(sp², Ferrocene),N,S(Thienyl)]^– Pincer Ligands

et al. 2012

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A study of the reactivity of [Pd({(η5‐C5H3)–CH=N–(CH2)n–(C4H3S)}Fe{η5‐C5H5})Cl], n = 2 (1e) or 1 (1f), with symmetric alkynes R1–C≡C–R1 (R1 = CO2Me, Et or Ph) has allowed us to achieve the di‐μ‐chloro‐bridged complexes [Pd({(MeO2C–C=C–CO2Me)(η5‐C5H3)–CH=N–(CH2)n–(C4H3S)}Fe{η5‐C5H5})μ‐Cl]2, n = 2 (3e) or 1 (3f), and the mononuclear derivatives [Pd({(MeO2C–C=C–CO2Me)(η5‐C5H3)–CH=N–(CH2)n–(C4H3S)}Fe{η5‐C5H5})Cl(PPh3)], n = 2 (4e) or 1 (4f), [Pd({(R1–C=C–R1)2(η5‐C5H3)–CH=N–(CH2)n–(C4H3S)}Fe{η5‐C5H5})Cl],R1 = CO2Me, n = 2 (5e) or 1 (5f), R1 = Et, n = 2 (6e) or 1 (6f), or R1 = Ph, n = 2 (7e), and [Pd({(Ph–C=C–Ph)2(η5‐C5H3)–CH=N–(CH2)–(C4H3S)}Fe{η5‐C5H5})Cl(PPh3)] (7f·1/2Ph–C≡C–Ph). With MeO2C–C≡C–CO2Me, mono‐ (3e, 3f, 4e and 4f) and bis‐insertion complexes (5e and 5f) were obtained, whereas for R1–C≡C–R1 with R1 = Et or Ph, only bis‐insertion products (6e, 6f, 7e and 7f) were isolated. These studies also proved that 1e and 1f, which have a labile Pd–S(thienyl) bond, are more prone to undergo the insertion of R1–C≡C–R1 (R1 = CO2Me, Et or Ph) than their analogues with [C(sp2, ferrocene), N, X]– [X = O, N(amine) or S(thioether)] pincer ligands.

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Improved synthesis of pincer ligand precursor, and synthesis and structural characterization of terphenyl scaffolded S–C–S palladium pincer complex

Cited by 5 publications

References 35 publications

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

C–H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas

Insertion of Symmetric Alkynes into the σ[Pd–C(sp², Ferrocene)] Bond of Palladacycles with [C(sp², Ferrocene),N,S(Thienyl)]^– Pincer Ligands

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Improved synthesis of pincer ligand precursor, and synthesis and structural characterization of terphenyl scaffolded S–C–S palladium pincer complex

Cited by 5 publications

References 35 publications

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

C–H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas

Insertion of Symmetric Alkynes into the σ[Pd–C(sp2, Ferrocene)] Bond of Palladacycles with [C(sp2, Ferrocene),N,S(Thienyl)]– Pincer Ligands

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Insertion of Symmetric Alkynes into the σ[Pd–C(sp², Ferrocene)] Bond of Palladacycles with [C(sp², Ferrocene),N,S(Thienyl)]^– Pincer Ligands