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Synthesis, structure, and supramolecular chemistry of three azide manganese complexes with 2, 6-Bis(benzimidazol-2-yl)pyridine

Three azide complexes with the tridentate ligand 2, 6-bis(benzimidazol-2- yl)pyridine (H2BBIP) were synthesized and their complicated supramolecular interactions were investigated with single-crystal X-ray diffraction. Interestingly, the complexes are assembled by bifurcated hydrogen bonding, double helical pi-pi stacking, or anion-pi stacking interactions of the benzimidazole rings by tuning the reaction conditions (temperature, ratio, solvent). Complex 1 is a mononuclear compound, namely, Mn(H 2BBIP)N3(CH3O)¡¤CH3OH. In its 3D supramolecular network, the nitrogen atom of the azide anion is acting as hydrogen bonding bifurcated acceptor. Complex 2 is a dinuclear compound, namely, Mn2(H2BBIP)2(N3) 2¡¤(H2O)0.5. The dinuclear unit is connected by intramolecular pi-pi stacking interactions. Furthermore, double helical pi-pi stacking interactions in the benzimidazole rings are observed. Complex 3, Mn2(H2BBIP)2(N 3)2¡¤CH3OH, can be formulated as a pseudopolymorph of complex 2, which exhibits intramolecular pi-pi stacking interactions as well as anion-pi interactions in the dinuclear unit. Copyright

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Spectroscopy and photoredox properties of soluble platinum(II) alkynyl complexes

Six complexes of platinum(II) with a terdentate pi-acceptor ligand, 2,6-(N-(n-hexyl)benzimidazol-2?-yl)pyridine), and different ethynylbenzene ligands were synthesized and investigated by means of optical absorption, luminescence, and time-resolved emission spectroscopy. These complexes display similar photophysical and electrochemical properties as previously investigated analogs with the 2,2?:6?,2?-terpyridine ligand. The energy of the luminescence band maximum is a function of the nature of the chemical substituents attached to the ethynylbenzene ligand, luminescence intensities and lifetimes correlate with the luminescence wavelength according to the energy-gap law. The emissive excited states of some of these complexes are quenched reductively with efficiencies near the diffusion-controlled limit, even for moderate electron donors such as phenothiazine or triphenylamine. A complex with a dimethylamine substituent attached to the ethynylbenzene ligand exhibits photophysical properties that are strongly dependent on the protonation state of the amine. A dimer complex with a diethynyl-substituted xanthene bridging ligand displays absorption and emission behavior that is essentially identical to that of some of the monomeric platinum complexes investigated in this work. Short Pt(II)-Pt(II) contacts are only observed in the crystal structure of a precursor complex. A key feature of the new complexes is their good solubility in common organic solvents, thanks to the presence of two hexyl chains that are attached to the terdentate ligands.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Synthesis, characterization, and antimicrobial properties of two cu(II) complexes derived from a benzimidazole ligand

Two copper(II) complexes, [Cu(L)2](ClO4)2] and [Cu(L)(bipy)](ClO4)2, were prepared and characterized by the spectroscopic and analytic methods, where L is N-butylbenzimidazole and bipy is 2,2?-bipyridine. Single crystals of [Cu(L)(bipy)](ClO4)2 suitable for X-ray diffraction study were obtained by slow diffusion of diethyl ether into a DMF solution of the complex and the complex was found to crystallize as [Cu(L)(bipy)](ClO4)2¡¤DMF. The asymmetric unit contains one [Cu(L) (bipy)]2+, two uncoordinated perchlorates, and one DMF solvate. Coordination geometry around Cu (II) is distorted square pyramidal with tau value of 0.31. Thermal properties of the complexes were examined by thermogravimetric analysis, indicating that the complexes are thermally stable to 310C. The metal complexes were screened for their in vitro antibacterial and antifungal activities Bacillus subtilis and Bacillus cereus (as Gram(+) bacteria), Escherichia coli, Enterobacter aerogenes, and Klebsiella pneumoniae (as Gram(?) bacteria), and Saccharomyces cerevisiae, Candida utilis, and Candida albicans (as yeasts). The complexes show antibacterial and antifungal activities against bacteria and yeasts.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Extracurricular laboratory:new discovery of (2,2¡ä-Bipyridine)dichloropalladium(II)

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Multiple Condensation Reactions Involving PtII/PdII?OH2, Pt?NH3, and Cytosine?NH2Groups: New Twists in Cisplatin?Nucleobase Chemistry

The coordination chemistry of the antitumor agent cisplatin and related complexes with DNA and its constituents, that is, the nucleobases, appears to be dominated by 1:1 and 1:2 adducts of the types cis-[Pta2(nucleobase)X] and cis-[Pta2(nucleobase)2] (a=NH3or amine; a2=diamine or diimine; X=Cl, OH or OH2). Here, we have studied the interactions of the putative 1:1 adducts cis-[Pta2(1-MeC-N3)(OH2)]2+(with a=NH3, a2=2,2?-bpy (2,2?-bipyridine), 1-MeC=model nucleobase 1-methylcytosine) with additional cis-[Pt(NH3)2(OH2)2]2+or its kinetically superior analogues [Pd(en)(OH2)2]2+(en=ethylenediamine) and [Pd(2,2?-bpy)(OH2)2]2+. Depending upon the conditions applied different compounds of different nuclearity are formed. Without exception they represent condensation products of the components, containing mu-1-MeC-H, mu-OH?, as well as mu-NH2?bridges. In the presence of Ag+ions, the isolated products in several cases display additionally Pt?Ag dative bonds. On the basis of the cytosine-containing structures established by X-ray crystallography, it is proposed that any of the feasible initial 1:1 nucleobase adducts of cisplatin could form dinuclear Pt complexes upon reaction with additional hydrolyzed cisplatin, thereby generating nucleobase adducts other than the presently established ones. Two findings appear to be of particular significance: First, hydrolyzed cisplatin can have a moderately accelerating effect on the formation of a secondary nucleobase product. Second, NH3ligands of the cisplatin moiety can be converted into bridging amido ligands following condensation with the diaqua species of cisplatin.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Benzimidazole: Small planar molecule with diverse anti-corrosion potentials

The cost of corrosion greatly impacts the economics of industrialized nations that a significant percentage could be equated in some way to a fraction of their GDP. The use of organic inhibitor compounds has proven to be one of the most practically effective methods for mitigating metal corrosion in various aggressive media. Most inhibitors play important roles in retarding corrosion due to the presence of sites of adsorption for metal surface bonding. Benzimidazoles being a unique stock of bicyclic compounds with a fused benzene/imidazole structure belong to this class of inhibitors. With their numerous therapeutic properties, their biological activities are also accompanied by safe and efficient corrosion protection abilities with negligible negative effects on man and his environment. Their superior inhibiting potency for metal corrosion over some other compounds is attributed to their rate of molecular adsorption at the metal/solution interface due to the presence of the nitrogen atom bearing the sp2 electron pair known to act as metal surface anchoring sites. This review covers older and most recent investigations related to the application of a number of benzimidazole derivatives as corrosion inhibitors for industrial metals in many simulated and real aqueous media. The mechanisms of corrosion protection for each inhibition system have also been highlighted via experimental and theoretical based approaches in acid, alkaline and near neutral media. The use of this class of compounds for microbial corrosion inhibition and sweet corrosion have also been proposed for future studies since reported research in this aspect are relatively scanty.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Electronic spectra of 1,2-diiminetricarbonylrhenium(I)chloride complexes with imidazole derivatives as ligands

A series of Re(CO)3(1,2-diimine)Cl complexes with bisimidazoles (BIIM) as 1,2-diimines have been synthesized and their electronic spectra studied. Compared with the absorption spectra of the free BIIM ligands, the spectra of the metal complexes display a shoulder at the low energy side of the intraligand (IL) bands. This additional absorption is assigned to the Re(I) to pi* (BIIM) metal-to-ligand charge transfer (MLCT) transition. Since imidazoles are weak pi-acceptor ligands, the MLCT band occurs at rather short wavelengths and is partially hidden by the intense IL bands of the BIIM moiety. The complexes are photoluminescent both at room temperature and at 77 K.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Comparison of the Reactivities of Neutral and Cationic Organopalladium Complexes toward CO, Isocyanides, and Olefins

Cationic solvent-coordinated organopalladium complexes [PdR(solvent)(L)2]+A- 2 (R = organic group, L = tertiary phosphine, A = counter anion such as BF4, PF6, and triflate) have been prepared by removal of the halide ligand X in neutral complexes. [PdR(X)(L)2] 1 with an equimolar amount of silver salt. The cationic complexes 2 show much greater rates of CO insertion than the parent neutral complexes 1. Comparison of the reactivities of 2 and of the other cationic complexes [PdMe(Y)(L)2]+ (Y = strongly coordinating ligand such as tertiary phosphine, pyridine, and isocyanide) toward CO insertion indicates that availability of the site for incoming CO is a dominant factor in determining their reactivities. In contrast, insertion of isocyanides into Pd-C bond is not hindered by occupation of the vacant site in the organopalladium complexes. Successive hetero-insertions of isocyanide and CO into Mc-Pd bond, i.e., CO insertion into the 1-iminoalkyl-Pd bond and isocyanide insertion into the acetyl-Pd, were realized. Olefins were found not to undergo the insertion into Pd-Me bond in phosphine-coordinated complexes, whereas insertion of methyl acrylate into the Me-Pd bond in a cationic complex having bipyridine ligand was observed.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Transition metal complexes of a benzimidazole ligand containing two heptyl chains: Synthesis, crystal structures, photophysical and thermal properties

In this study, a benzimidazole ligand (L) containing two heptyl chains and its transition metal [Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] complexes were prepared and characterized by spectroscopic and analytical methods. Molecular structures of the complexes [Mn(L)Cl2], [Co(L)Cl2], [Cu(L)Cl2] and [Zn(L)Cl2] were determined by X-ray diffraction studies. In the structure of the complexes, metal ions are five-coordinate with distorted square pyramidal geometry. X-ray structural data showed the alignment of the heptyl aliphatic chains and the bond angles between the two coordinated chloride angles (Cl-M-Cl) have an effect on the crystal packing of the complex molecules. The ligand-based emission band showed a red-shift in the spectra of [Fe(L)Cl2] and [Zn(L)Cl2] complexes. Finally, thermal behaviours of the ligand and its metal complexes were studied under nitrogen atmosphere. The complexes were found to decompose at higher temperatures than that of the ligand.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Ni(ii)-N?NN? pincer complexes catalyzed dehydrogenation of primary alcohols to carboxylic acids and H2 accompanied by alcohol etherification

Acceptorless dehydrogenation of alcohols to carboxylic acid derivatives catalyzed by a transition metal complex is an important reaction in modern organic synthesis and catalysis, for which nickel complexes have rarely been developed. Herein we report three Ni(ii) complexes bearing pyridine-based N?NN? type pincer ligands, which catalyze the acceptorless dehydrogenation of primary alcohols to carboxylic acids under anhyrous conditions. The complex [NiCl2(L3)] 3 (L3 = 2,6-bis(diethylaminomethyl)pyridine) displays the best catalytic reactivity, catalyzing the primary alcohols to carboxylic acids and H2 in good yields (40-90%). Further investigation reveals that an unexpected alcohol etherification occurs, which gives the second oxygen atom for the formation of the carboxylic acid. Our results give a thread for the design of new nickel complexes without phosphine and N-heterocycle carbene ligands for the acceptorless oxidation of alcohols.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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NOVEL GOLD(III) COMPLEXES CONTAINING N-HETEROCYCLIC CARBENE LIGAND, SYNTHESIS, AND THEIR APPLICATIONS IN CANCER TREATMENT AND THIOL DETECTION

Provided herein is a method of synthesis of Au(III)-NHC complexes, a pharmaceutical composition comprises thereof. Also provided herein are the methods for the treatment and prevention of cancer/tumor in patients in need thereof by the administration of the Au(III)-NHC complexes. Also provided is method of detecting thiol in a biological system. The Au(III)-NHC complexes possess anticancer activity such as the induction of cell death, inhibition of cellular proliferation, inhibition of thioredoxin reductase activity, and inhibition of tumor growth in vivo.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method