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This report examines the replacement of the imine and pyridine functionalities of the ubiquitous bis(imino)pyridine ligand with various heterocycles. The synthesis of a new class of ligand based around thiazole is described; 2,4-bis[1-(arylimino)ethyl]thiazole (aryl=Ph, 1a; Dipp, 1b) and 2,5-bis[1-(arylimino)ethyl]thiazole (aryl=Ph, 1c; Dipp, 1d) have been prepared in good yield and fully characterized. The coordination chemistry of these ligands with chromium, iron, and cobalt is explored, and the potential of these complexes as ethylene oligomerization initiators is assessed. The chromium complex 2a shows an extremely unusual alternating distribution of higher alpha-olefin products, which has been previously observed on only one occasion. Both series of products, C4n and C4n+2, show Schulz-Flory behavior but with distinctly different k values. The new ligand 2,5-bis[1-(phenylimino)ethyl]-1-methylpyrrole (1e) is reported along with the attempted synthesis of some corresponding iron complexes. The complexation of chromium by 2,5-bis-(phenyliminomethyl)thiophene (1f) is also described, and this material was screened for ethylene oligomerization activity, detailed studies indicating that the ligand may be labile under catalytic conditions. A number of other known heterocyclic ligands incorporating pyrazolyl and benzimidazole functionalities have also been explored with iron, and for the first time their potential to facilitate ethylene oligomerization was assessed. All complexes have been tested via activation with MMAO-3A and AlEt 3/[Ph3C][Al(OtBuF)4].

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

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In this paper, we synthesized complexes of imidazole derivatives. The structures of complexes Ni(L1)2(CNS)2 (complex 1), Zn(L2)2(CNS)2 (complex 2) and MnL3Cl2 (complex 3) were determined by X-ray diffraction in those complexes. The space groups of complex 1, 2 and 3 are C2c/c, P-1 and P21/n, respectively. Ni (II), Zn (II) ions are coordinated by four nitrogen atoms of ligands and two nitrogen atoms of thiocyanate. Mn(II) ion is coordinated by three nitrogen atoms of ligand and two chlorine atoms. Single crystal X-ray studies on complex 2 and complex 3 indicate that the molecules of the complexes 2 and 3 link together through intermolecular NH?S hydrogen bonds and NH?Cl hydrogen bonds, respectively. The DFT (Density Functional Theory) and luminescent properties of these complexes are discussed. The calculated results are in good agreement with the experimental data.

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

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Penta-coordinated mononuclear copper(II) complex of tridentate 2,6-bis-(benzimidazolyl)pyridine (L) formulated as [Cu(L)(H2O)2](NO3)2, 1 was synthesized and isolated in pure form. The complex was characterized by physico-chemical and spectroscopic methods, as well as single crystal X-ray diffraction analysis. The structural study shows the metal in a highly distorted square pyramidal geometry [trigonality index tau = 0.1425] that comprises two aqua molecules in the first coordination sphere. The crystal packing of 1 shows a 3D polymer formed through H-bonds involving aquo ligands, NH benzimidazole groups and nitrate anions. On reaction with pseudohalides in acetonitrile at ambient temperature complex 1 changed to mono cationic copper(II) derivatives [Cu(L)(X)(H2O)]NO3 [X = SCN- (2a) and N3- (2b)]. These copper(II) complexes have been isolated from the reaction mixtures and characterized by physico-chemical and spectroscopic tools. The interaction of complex 1 with calf thymus DNA (CT-DNA) has been investigated by using absorption and emission spectral studies, the binding constant (Kb) and the linear Stern-Volmer quenching constant (Ksv) have been determined.

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

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In this work, the effects of ligand field strength as well as the metal coordination geometry on magnetic anisotropy of pentacoordinated CoII complexes have been investigated using a combined experimental and theoretical approach. For that, a strategic design and synthesis of three pentacoordinate CoII complexes [Co(bbp)Cl2]·(MeOH) (1), [Co(bbp)Br2]·(MeOH) (2), and [Co(bbp)(NCS)2] (3) has been achieved by using the tridentate coordination environment of the ligand in conjunction with the accommodating terminal ligands (i.e., chloride, bromide, and thiocyanate). Detailed magnetic studies disclose the occurrence of slow magnetic relaxation behavior of CoII centers with an easy-plane magnetic anisotropy. A quantitative estimation of ZFS parameters has been successfully performed by density functional theory (DFT) calculations. Both the sign and magnitude of ZFS parameters are prophesied well by this DFT method. The theoretical results also reveal that the alpha ? beta (SOMO-SOMO) excitation contributes almost entirely to the total ZFS values for all complexes. It is worth noting that the excitation pertaining to the most positive contribution to the ZFS parameter is the dxy ? dx2-y2 excitation for complexes 1 and 2, whereas for complex 3 it is the dz2 ? dx2-y2 excitation.

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

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We show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L?)](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2·C3H6O (1), [Fe(H2L3)(Me3bpp)](ClO4)2·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2·3C3H6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a single-crystal-to-single-crystal transformation. This guest extrusion process is accompanied by a spin switch, from HS to LS.

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

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Two bis-tridentate pincer complexes [Ru(H2bip)(Mebib)](PF6)2 (1(PF6)2) and [Ru(H2bip)(H2bib)](PF6)2 (2(PF6)2) were prepared and studied, where H2bip is 2,6-bis(benzimidazol-2-yl)pyridine, Mebib is the 2-deprotonated 1,3-bis(N-methylbenzimidazol-2-yl)benzene, and H2bib is 2-deprotonated 1,3-bis(benzimidazol-2-yl)benzene. These complexes were isolated as cyclometalated Ru(III) salts with a [(NCN)(NNN)] coordination due to a low Ru(III/II) redox potential. Complex 1(PF6)2 has two N?H protons on the NNN ligand side, while complex 2(PF6)2 has four N?H protons. Absorption spectral analysis showed that two deprotonation steps were distinguished for 1(PF6)2 with pKa1 and pKa2 of 3.46 and 5.88, respectively. In comparison, four deprotonation steps were observed for 2(PF6)2 with four pKa values of 3.45, 5.95, 8.95, and 10.98, respectively. When the solution was changed from acidic to basic, the Ru(III/II) redox wave of 1(PF6)2 and 2(PF6)2 shifted from +0.20 V vs Ag/AgCl to a less positive region by 540 and 850 mV, respectively. These studies suggest that the electronic absorption and electrochemical properties of these complexes are very sensitive to pH effect.

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

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Some new mixed-ligand cyanonitrosyl complexes of manganese(0), obtained from the interaction of tetracyanodinitrosylmanganate(0) anion, [Mn(NO) 2(CN)4]2-, with benzothiazole (BZT), benzimidazole (BZL), 2-(4?-pyridyl)benzimidazole (4?-PYBZ), 1,3-bis(2?-benzimidazyl)benzene (BBZLBZ) and 2,6-bis(2? -benzimidazyl)pyridine (BBZLPY), are described. The products, which have been characterized by elemental analyses, molar conductance and magnetic measurements, ESR, electronic and infrared spectral studies, have the compositions, [Mn(NO)2(CN)2(L)2]·H 2O {where L=BZT (1), BZL (2) or 4?-PYBZ (3)}, [Mn(NO) 2(CN)2(BBZLBZ)]2·H2O (4) and [Mn(NO)2(CN)2(BBZLPY)]·H2O (5). Manganese(0) has a low-spin {Mn(NO)2}7 electron configuration in these paramagnetic complexes. Suitable structures have been proposed for these complexes.

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

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The complex [Fe(bzimpy)2](BPh4)2·nH2O exists with n=4 (1), n=2 (2) and n=0 (3). The tetrahydrate is a spin crossover system with the transition centred at room temperature. The dihydrate, prepared from a solution with reduced water content, is a high-spin complex over the entire temperature region. The anhydrous complex, prepared by overheating of 1, remains high-spin. Unlike that in the sulphate (4) and perchlorate (5) analogues, the spin crossover in 1 is complete. The magnetic data fitting procedure yields the set of magnetic parameters describing the spin crossover quantitatively: g=2.54, J/k= -226 K, DeltaH=14.9 kJ mol-1 and DeltaS=45 J K-1 mol-1.

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

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2,6-Bis(benzimidazol-2-yl)pyridine (BBP/CSFA-0) was identified in a CPE-based screening as a selective inhibitor of the in vitro bovine viral diarrhea virus (BVDV) replication. The EC50-values for the inhibition of BVDV-induced cytopathic (CPE) effect, viral RNA synthesis and the production of infectious virus were 0.3±0.1muM, 0.05±0.01muM and 0.3±0.04muM, respectively. Furthermore, BBP/CSFA-0 inhibits the in vitro replication of the classical swine fever virus (CSFV) with an EC50 of 0.33±0.25muM. BBP/CSFA-0 proved in vitro inactive against the hepatitis C virus, that belongs like BVDV and CSFV to the family of Flaviviridae. Modification of the substituents on the two 1H-benzimidazole groups of BBP resulted in analogues equipotent in anti-BVDV activity (EC50=0.7±0.1muM), devoid of cytotoxicity (S.I.=142). BBP resistant BVDV was selected for and was found to carry the I261M mutation in the viral RNA-dependent RNA polymerase (RdRp). Likewise, BBP-resistant CSFV was selected for; this variant carries either an I261N or a P262A mutation in NS5B. Molecular modeling revealed that I261 and P262 are located in a small cavity near the fingertip domain of the pestivirus polymerase. BBP-resistant BVDV and CSFV proved to be cross-resistant to earlier reported pestivirus inhibitors (BPIP, AG110 and LZ37) that are known to target the same region of the RdRp. BBP did not inhibit the in vitro activity of recombinant BVDV RdRp but inhibited the activity of BVDV replication complexes (RCs). BBP interacts likely with the fingertip of the pestivirus RdRp at the same position as BPIP, AG110 and LZ37. This indicates that this region is a “hot spot” for inhibition of pestivirus replication.

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

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Three novel cisplatin analogues were synthesized, designed according to an approach which violates the “classical” structure-activity relationship, by replacing the diamine ligands with a planar N donor heterocycle giving a sterically hindered complex. Moreover, the sterical hindrance of antitumor drug candidates potentially makes them less susceptible to deactivation by sulphur-containing proteins and helping to overcome resistance mechanisms. The resulting mononuclear complexes of sterically hindered polidentate heterocyclic N ligands [PtCl(bbp)]Cl (1) [bbp = 2,6-bis(2- benzimidazolyl)pyridine], [PtCl2(dptdn)](H2O) (2) [dptdn = sodium 5,6-diphenyl-3-(2?-pyridyl)-1,2,4-triazine-4?, 4??-disulfonate] and [(dptdn)(dpt)Pt]Cl2(H2O) (3) [dpt = 5,6-diphenyl-3-(2?-pyridyl)-1,2,4-triazine] have been prepared and structurally characterised. Both neutral and ionic complexes are present, with monofunctional (1) and bifunctional Pt(II) moieties (2) and coordinatively saturated Pt(II) ions in the mixed ligand complex (3), whose size and shape enable them to behave as novel scaffolds for DNA binding. All complexes were tested “in vitro” for their biological activity on human HT29 colorectal carcinoma and HepG2 hepatoma cells. The complexes (1) and (3), endowed with a positive charge, showed a potent cytotoxic activity and reduced cell viability with an efficacy higher than that of cisplatin; whilst the neutral bifunctional compound (2) was inactive. IC50 values have been calculated for the active compounds. The cytotoxic effects were confirmed by the accumulation of treated cells in subG0/G1 phase of cell cycle, by the loss of mitochondrial potential (Deltapsim) and by the chromatin condensation or fragmentation observed by means of fluorescence microscopy after Hoechst 33258 nuclear staining. A study on intracellular platinum uptake in HT29 cell line has been also performed and data obtained strongly suggest that the cytotoxicity of new tested complexes reported in this work is based on a different pharmacodynamic pattern with respect to cisplatin.

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