- Heteroleptic copper(i) halides with triphenylphosphine and acetylthiourea: Synthesis, characterization and biological studies (experimental and molecular docking)
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Nine new copper complexes with the general formula [CuX(TPP)n(ATU)3-n] (where X = Cl, Br, and I, ATU = acetylthiourea, TPP = triphenylphosphine and n varies as 0, 1 and 2) were synthesized in a simple fashion, by changing the ratio of the ligands. The synthesized complexes were characterized by techniques, such as FT-IR and NMR spectroscopy, CHNS elemental analysis and single crystal X-ray technique. The XRD technique showed the monodentate behavior of TPP and ATU. The synthesized compounds were utilized in different biological assays, which showed anti-bacterial, anti-fungal, anti-lieshmanial, anti-oxidant and cytotoxic properties against brine shrimps. In parallel, molecular docking was carried out to decipher the binding conformation and chemical interactions of the compounds in the active binding pockets of biological drug targets against bacterial pathogens and lieshmanial parasite, as well as a cancer target. All these analyses revealed compounds [CuCl(TPP)(ATU)2] and [CuI(TPP)(ATU)2] to be the most effective molecules of the series. Molecular docking indicated that hydrogen bonding and hydrophobic pi-interactions play important role for the activities of complexes with ligands TPP/ATU ratio of 1/2.
- Khan, Syed Ishtiaq,Ahmad, Sajjad,Altaf, Ataf Ali,Rauf, Muhammad Khawar,Badshah, Amin,Azam, Syed Sikander,Tahir, Muhammad Nawaz
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- Synthesis, characterization, theoretical, and antimicrobial studies of indenoquinoxalin-based ligands and their reactions with CuBr(PPh3)3
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A series of three ligands were derived from the condensation of indeno[1,2-b]quinoxalin-11-one and hydrazines (L1 from hydrazine, L2 from phenylhydrazine and L3 from thiosemicarbazide). The three ligands were stirred with CuBr(PPh3)3 in dichloromethane; no reaction was observed except in the case of L3, providing a complex with the formula CuBr(PPh3)2(κS-L3) (Cu-L3). Crystal structure of the complex revealed that the central copper atom in the molecule is coordinated to two triphenylphosphine groups, a bromine atom and to the indeno[1,2-b]quinoxalin-11-ylidenecarbothioamidohydrazide (L3) ligand via S atom; forming a distorted tetrahedral geometry around it. In general, Cu-L3 complex has shorter Cu-P bond lengths compared to the parent complex which suggest less steric hindrance in Cu-L3. None of the three ligands were able to use the nitrogen atoms as donating atoms due to their highly engagement in hydrogen-bonding as observed in the crystal structure of Cu-L3 as well as the theoretical calculations. Moreover, theoretical calculation indicated that Cu-N interactions were weak with long distances beyond the typical bonding distances. Antimicrobial screening against a range of strains showed selective inhabitations of indeno[1,2-b]quinoxalin-11-one, L1 and L3 against S. aureus strain. Moreover, the introduction of the copper fragment to L3 did not cause any significant improvements to the antimicrobial properties of L3.
- Babgi, Bandar A.,Bawazeer, Musab,Alzaidi, Najah A.,Arshad, Muhammad N.,Jedidi, Abdesslem,Bataweel, Noor M.,Al-Hejin, Ahmed M.,Hussien, Mostafa A.
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- Mononuclear copper(i) complexes of triphenylphosphine and: N, N ′-disubstituted thioureas as potential DNA binding chemotherapeutics
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In this work, nine new mixed-ligand complexes with the general formula [CuBr(TPP)2Tu1-9] were synthesized. The copper(i) complexes of triphenylphosphine (TPP) and different N,N′-disubstituted thioureas (Tu) were characterized via spectroscopic techniques including Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H, 13C, and 31P NMR), and single-crystal X-ray diffraction (SC-XRD). The complexes were synthesized via the direct reaction of bromo(tris(triphenylphosphine)copper(i)) [BrCu(PPh3)3] precursor and thiourea ligand solution under ambient conditions. Complexes 1, 2 and 3 crystallized in a triclinic system with the P1 space group. Each complex is mononuclear, and the copper atom is tetrahedrally attached to two TPP groups through the phosphorous atom, one thiourea molecule through the sulfur atom and one bromine atom. The synthesized compounds were docked with a DNA macromolecule to predict their binding site and it was found that all molecules showed favorable binding to the DNA minor grooves. The DNA interaction studies of the representative complexes demonstrated their efficient DNA binding affinities. Based on the docking and DNA interaction results, complex 7 was found to be the best binder with a docking affinity of 382.2 kJ mol-1 and binding constant of 3.96 × 104 M-1. This compound tends to interact with the minor groove through the bromine atom positioning the side triphenylphosphine rings along the X-axis of the groove while keeping the 1-(2-chlorobenzyl)-3-(3-(trifluoromethyl)phenyl)thiourea ring on the outside.
- Khan, Syed Ishtiaq,Ahmad, Sajjad,Khan, Inayat Ali,Badshah, Amin,Rauf, Muhammad Khawar,Putejo, Jahangir Ali,Siddiq, Muhammad Nasir,Kausar, Samia,Altaf, Ataf Ali
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- Optimized Immobilization Strategy for Dirhodium(II) Carboxylate Catalysts for C?H Functionalization and Their Implementation in a Packed Bed Flow Reactor
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Herein we demonstrate a packed bed flow reactor capable of achieving highly regio- and stereoselective C?H functionalization reactions using a newly developed Rh2(S-2-Cl-5-CF3TPCP)4 catalyst. To optimize the immobilized dirhodium catalyst employed in the flow reactor, we systematically study both (i) the effects of ligand immobilization position, demonstrating the critical factor that the catalyst-support attachment location can have on the catalyst performance, and (ii) silica support mesopore length, demonstrating that decreasing diffusional limitations leads to increased accessibility of the active site and higher catalyst turnover frequency. We employ the immobilized dirhodium catalyst in a simple packed bed flow reactor achieving comparable yields and levels of enantioselectivity to the homogeneous catalyst employed in batch and maintain this performance over ten catalyst recycles.
- Davies, Huw M. L.,Hatridge, Taylor A.,Jones, Christopher W.,Liu, Wenbin,Yoo, Chun-Jae
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- Synthesis, structures, DNA-binding and anticancer activities of some copper(I)-phosphine complexes
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Copper(I) complexes with a phenanthroline-phosphine set of ligands were synthesized by refluxing methanolic solutions of CuBr2 with at least a four fold molar excess of the phosphine ligands, followed by the treatment of the formed {CuBr(PR3)3 complexes [R = phenyl (1a), 4-fluorophenyl (1b), cyclohexyl (1c) or 4-methoxyphenyl (1d)]} with 1 molar equivalent of 1,10-phenanthroline in DCM. The tris(4-methoxyphenyl)phosphine ligand afforded the complex [Cu(P[C6H4-4-OMe]3)2(phen)]Br (2d), while the other phosphines produced complexes with the general formula CuBr(PR3)(phen) [R = phenyl (2a), 4-fluorophenyl (2b) or cyclohexyl (2c)]. The new complexes were characterized by elemental analysis, 31P NMR spectroscopy and mass spectrometry. Additional confirmation of the structures of 1b, 2b, 2c and 2d were determined by single crystal X-ray diffraction. A DNA-binding study of the complexes 2a–2d against ct-DNA showed binding constant values that correspond to the intercalation mode of binding. The notable variations in the binding constants of the complexes suggest some contribution from the phosphine ligands. The lipophilicity of the complexes was evaluated theoretically and the calculated log P value of complex 2d is positive and high, being in the same range of relatively easy membrane penetrating drugs. The calculated log P values of complexes 2a–2c are negative, indicating a low membrane permeability. Complexes 2a–2d were examined against four different cancer cell lines. The choice of the phosphine ligand appears to influence the copper(I)-phosphine anticancer activities against the different cancer cell lines. The data suggested that complexes 2a and 2d show potential anticancer activity against prostate and breast cancers. The four copper complexes were docked against four different proteins associated with prostate or breast cancers activities, highlighting some of the structural-DNA interactions.
- Mashat, Khlood H.,Babgi, Bandar A.,Hussien, Mostafa A.,Nadeem Arshad, Muhammad,Abdellattif, Magda H.
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- Dna-binding and cytotoxicity of copper(I) complexes containing functionalized dipyridylphenazine ligands
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A set of copper(I) coordination compounds with general formula [CuBr(PPh3 )(dppz-R)] (dppz-R = dipyrido[3,2-a:2’,3’-c]phenazine (Cu-1), 11-nitrodipyrido[3,2-a:2’,3’-c]phenazine (Cu-2), 11-cyanodipyrido[3,2-a:2’,3’-c]phenazine (Cu-3), dipyrido[3,2-a:2’,3’-c]phenazine-11-phenone (Cu-4), 11,12-dimethyldipyrido[3,2-a:2’,3’-c]phenazine (Cu-5)) have been prepared and characterized by elemental analysis,1H-NMR and31P-NMR spectroscopies as well as mass spectrometry. The structure of Cu-1 was confirmed by X-ray crystallography. The effect of incorporating different functional groups on the dppz ligand on the binding into CT-DNA was evaluated by absorption spectroscopy, fluorescence quenching of EtBr-DNA adducts, and viscosity measurements. The functional groups affected the binding modes and hence the strength of binding affinities, as suggested by the changes in the relative viscosity. The differences in the quenching constants (Ksv) obtained from the fluorescence quenching assay highlight the importance of the functional groups in altering the binding sites on the DNA. The molecular docking data support the DNA-binding studies, with the sites and mode of interactions against B-DNA changing with the different functional groups. Evaluation of the anticancer activities of the five copper compounds against two different cancer cell lines (M-14 and MCF-7) indicated the importance of the functional groups on the dppz ligand on the anticancer activities. Among the five copper complexes, the cyano-containing complex (Cu-3) has the best anticancer activities.
- Alsaedi, Sammar,Babgi, Bandar A.,Abdellattif, Magda H.,Arshad, Muhammad N.,Emwas, Abdul-Hamid M.,Jaremko, Mariusz,Humphrey, Mark G.,Asiri, Abdullah M.,Hussien, Mostafa A.
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- Quinazolinone and benzotriazinone compounds with cholinergic muscarinin M1 receptor positive allosteric modulator activity
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The present invention provides a compound which has a cholinergic muscarinic M1 receptor positive allosteric modulator activity and may be useful as a medicament such as an agent for the prophylaxis or treatment of Alzheimer's disease, schizophrenia, pain, sleep disorder, Parkinson's disease dementia, Lewy body dementia and the like. The present invention relates to a compound represented by the formula (I) or a salt thereof. In the formula (I), each symbol is as described in the attached specification.
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(2020/02/20)
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- Synthesis, Antibacterial and Antileishmanial Activity, Cytotoxicity, and Molecular Docking of New Heteroleptic Copper(I) Complexes with Thiourea Ligands and Triphenylphosphine
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A series of copper(I) complexes with triphenylphosphine and N-acyl-N′-arylthioureas were synthesized and characterized by elemental analysis and IR and NMR (1H, 13C, 31P) spectroscopy. The thiourea ligands and their copper
- Saeed,Larik,Jabeen,Mehfooz,Ghumro,El-Seedi,Ali,Channar,Ashraf
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p. 541 - 550
(2018/04/24)
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- Rhodium nanoflowers stabilized by a nitrogen-rich PEG-tagged substrate as recyclable catalyst for the stereoselective hydrosilylation of internal alkynes
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Morphology and size controllable rhodium nanoparticles stabilized by a nitrogen-rich polyoxyethylenated derivative have been prepared by reduction of RhCl 3 with NaBH4 in water at room temperature and fully characterized. The flower-like Rh NPs are effective and recyclable catalysts for the stereoselective hydrosilylation of challenging internal alkynes and diynes, affording the (E)-vinylsilanes in quantitative yields for a wide range of substrates. The insolubility of the nanocatalyst in diethyl ether allows its easy separation and recycling.
- Guo, Wusheng,Pleixats, Roser,Shafir, Alexandr,Parella, Teodor
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supporting information
p. 89 - 99
(2015/01/30)
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- Methods and systems for preparing fused heterocyclic compounds using copper(I) catalysts
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A copper(I)-catalyzed procedure for the synthesis of benzo[b]heterocycles. This protocol can be used to synthesize a variety of 2-arylbenzo[b]furans and indoles in good to excellent yields. This method can tolerate a variety of functional groups, does not require the use of expensive additives and is palladium-free.
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(2009/01/24)
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- Methods of 1,3-enyne preparation using copper (I) catalysts
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A copper(I) bi-dentate ligand complex-catalyzed procedure for synthesis of 1,3-enynes. The methods and/or systems of this invention afford a variety of enynes, tolerate a variety of sensitive functional groups, and can be employed without resort to expensive palladium reagents.
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(2009/01/24)
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- Structural and solid state31P NMR studies of the four-coordinate copper(I) complexes [Cu(PPh3)3X] and [Cu(PPh 3)3(CH3CN)]X
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The tris(triphenylphosphine)copper(I) complexes [(PPh3) 3CuX] for X = Cl (1), Br (2), I (3), ClO4 (4), BF 4 (5), [(PPh3)3CuCl]·CH3CN (1a), [Cu(PPh3)3(CH3CN)]X for X = ClO 4 (6), BF4 (7), and [Cu(PPh3) 3(CH3CN)]X·CH3CN for X = SiF5 (8), PF6 (9) have been studied by solid state 31P CP/MAS NMR spectroscopy together with single crystal X-ray diffraction for compounds (6)-(9), the latter completing the availability of crystal structure data for the series. Compounds (1)-(5) form an isomorphous series in space group P3 (a ～ 19, c ～ 11 A) with three independent molecules in the unit cell, all disposed about 3-fold symmetry axes. Average values (with estimated standard deviations) for the P-Cu-P, P-Cu-X bond angles and Cu-P bond lengths in compounds (1)-(3) are 110.1(6)°, 108.8(6)° and 2.354(8) A and 115.2(6)°, 102.8(9)° and 2.306(9) A for compounds (4) and (5). For the acetonitrile solvated compound (1a), the corresponding parameters are 115(4)°,103(3)° and 2.309(3) A. The solid state 31P CP/MAS NMR quadrupole distortion parameters, dvCu, for (1)-(3) and (1a) are all less than 1 × 109 Hz2, despite the changes in donor properties of the halide in (1)-(3), and the coordination geometry of the P3CuX core in (1a). Change of anion to ClO 4- and BF4- in compounds (4) and (5) results in a significant increase of dvCu to 4.4-5.2 109 Hz2 and 5.2-6.0 × 109 Hz2, respectively. Compounds (6) and (7) crystallise as isomorphous [Cu(PPh3) 3(CH3CN)]X salts in space group Pbca, (a ～ 17.6, b ～22.3, c ～24.2 A), while compounds (8) and (9) crystallize as isomorphous acetonitrile solvated salts [Cu(PPh3)3(CH 3CN)]X·CH3CN in space group P1 (a ～ 10.5, b ～ 13.0, c ～19.5 A, a ～ 104, β ～ 104, γ ～ 94°). The P3CuN angular geometries in all four compounds are distorted from tetrahedral symmetry with average P-Cu-P, P-Cu-N angles and Cu-P bond lengths of 115(4)°, 103(4)° and 2.32(1) A, with dv Cu ranging between 1.3 and 2.5 × 109 Hz2. The solid state 29Si CP/MAS NMR spectrum of the pentafluorosilicate anion in compound (8) is also reported, affording 1J(29Si, 19F) = 146 Hz. The Royal Society of Chemistry 2005.
- Hanna, John V.,Boyd, Sue E.,Healy, Peter C.,Bowmaker, Graham A.,Skelton, Brian W.,White, Allan H.
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p. 2547 - 2556
(2007/10/03)
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- Thermochemistry of adducts of some bivalent transition metal bromides with triphenylphosphine
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The compounds [MBrm(L)n] (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(I) or Zn(II); L = triphenyphosphine (tpp); m = 1 or 2; n = 1.5, 2 or 3) were synthesized and characterized by melting points, elemental analysis, thermal analysis and electronic and IR spectroscopy. The enthalpies of dissolution of the adducts, metal(II) bromides and triphenylphosphine in methanol or in a solution of 10% (v/v) triethanolamine, 40% (v/v) acetonitrile and 50% (v/v) methanol were measured and by using thermochemical cycles, the following thermochemical parameters for the adducts, have been determined: the standard enthalpies for the Lewis acid/base reaction (ΔrH θ), the standard enthalpies of formation (Δ fHθ), the standard enthalpies of decomposition (ΔDHθ), the lattice standard enthalpies (ΔMHθ) and the standard enthalpies of the Lewis acid/base reaction in the gaseous phase (ΔrH θ(g)). The mean bond dissociation enthalpies of the metal(II)-phosphorus bonds (D?(M-P)) have been estimated.
- Dunstan, Pedro Oliver
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p. 100 - 105
(2008/10/09)
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- Solution equilibria of tertiary phosphine complexes of copper(I) halides
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The solution equilibria in benzene of arylphosphine complexes of the type LmCunXn (L = Ph3P, MePh2P; X = Cl, Br, I; m:n = 3:1, 4:2, 3:2, 2:2, 4:4) have been investigated by using UV spectrometry and vapor pressure osmometry. The halogen appears to have only a minor effect on the dissociation. A detailed analysis of the chloride complexes shows that ligand dissociation of the L3CuCl complexes is also accompanied by dimerization of the coordinately unsaturated copper(I) complexes through halogen bridging. However, the dimeric and tetrameric species formed by halogen bridging are found to be significant species in solution only when the ratio of L to CuCl is less than 3:1. An equilibria system is proposed with equilibrium constants derived from the modeling of the experimental data. The constants for the single ligand dissociation from (Ph3P)3CuCl and (MePh2P)3CuCl are 2 × 10-2 and 2 × 10-4, respectively. With the much greater dissociation of the Ph3P complex, the (Ph3P)2CuCl species is the dominant form in a benzene solution made from the solid-state (Ph3P)3CuCl complex. Solution profiles of different ratios of L to CuCl are generated to show how various species present in solution vary with concentration. The stability of the LmCunCln complexes (Ph3P ? MePh2P) toward ligand dissociation is attributed to greater steric interactions of Ph3P in comparison to MePh2P.
- Fife, Dennis J.,Moore, William M.,Morse, Karen W.
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p. 1684 - 1691
(2008/10/08)
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