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Monocyclopentadienyl complexes in which the cyclopentadienyl system bears at least one bridged donor and at least one aryl group and a catalyst system comprising at least one of the monocyclopentad ienyl complexes, and also processes for preparing them, the use of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyole­ fins by polymerization or copolymerization of olefins in the presence of the catalyst system and the preparation of the associated cyclopentadienyl system.

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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 advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts – multimetallic catalysis – can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts – (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium – enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.

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

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An unreported product outcome from an intended Sonogashira coupling is presented. The generality of this finding has been demonstrated by screening of a range of pre-catalysts. Mechanistic studies are consistent with the tetra-aryl benzene product forming by interception of the aryl halide oxidative addition intermediate by repeated acetylene insertion.

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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

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A series of PbIImaterials containing the highly anisotropic tridentate ligand 2,6-bis(benzimidazol-2-yl)pyridine (bbp) and [Au(CN)2]?, Hg(CN)2or halide bridging units, [Pb(bbp)Br2]·2H2O, Pb(bbp)I2, [Pb(bbp)I]2(mu-I)[Au(CN)2], [Pb(bbp)Br]2(mu-Br)[Au(CN)2], [Pb(bbp)Br2][Hg(CN)2], Pb(bbp)Cl[Au(CN)2]·0.25H2O and Pb(H2O)(bbp)2[Au(CN)2]2, have been prepared, structurally characterised and investigated spectroscopically by207Pb solid-state NMR spectroscopy. Of these, five possess similar coordination geometries, providing an ideal series to investigate structural parameters as indicators for stereochemical activity by correlation with the207Pb chemical shift span parameter (Omega). The bond length of the substituent opposite to the stereochemically active lone pair and the angle between axial ligands were found to correlate weakly with Omega for these compounds (R2= 0.85 and 0.66, respectively) and an expanded set of compounds with varying components and structures (R2= 0.60 and 0.67, respectively), which indicates that these (or similar) structural parameters or Omega can be used to estimate the degree of lone-pair activity. Compounds were also found to be highly birefringent with values ranging from 0.31(5) for Pb(H2O)(bbp)2[Au(CN)2]2to 0.660(4) for [Pb(bbp)Br2]·2H2O, the latter being amongst the most birefringent compounds reported.

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

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Steady-state and pulse radiolysis studies of three complementary palladium(II) complexes, . Cl and (bipy = 2,2′-bipyridine, HypO = 4-hydroxy-L-prolinate) have been performed.The site of attack of e(1-) (aq) and OH. radical in these complexes and the effect of gamma irradiation on the optical activity of the complexes containing HypO has been assessed using optical absorption and circular dichroism techniques.The steady-state gamma irradiation results for and (1+) are significantly different from those of with both e(1-) (aq) and OH..Precipitation of fine metal palladium particles is observed in the reaction of e(1-) (aq) with .Formation of a new optically active species is observed in the reaction of OH. with both and (1+) accompanied by a substantial loss in optical activity of the parent complexes.The substitution of one amino acid ligand in with bipy leads to a change in the site of attack of e(1-) (aq) from the metal centre in the binary complex to the bipy leads to a change in the site of attack of e(1-) (aq) from the metal centre in the binary complex tot he bipy ring in the ternary complex.The pulse-radiolysis results support inferences drawn from the steady-state gamma-radiolysis investigation.

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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 reactivity of the metalloligand [Pt2(mu-S) 2(PPh3)4] towards a wide range of platinum(II) and palladium(II) chloride complex substrates [L2MCl2] has been explored, using the technique of electrospray ionisation mass spectrometry to directly analyse reaction solutions. In the majority of cases, products are formed by addition of the ML22+ fragment to the {Pt 2S2} core, giving trinuclear species [Pt 2(mu-S)2(PPh3)4ML 2]2+. The adducts with Pt(diene) [diene=cyclo-octa-1,5- diene (cod), norbornadiene], Pd(cod), Pd(bipy) (bipy=2,2?- bipyridine), Pt(PMe3)2 and Pt(PTA)2 (PTA=phosphatriaza-adamantane) moieties were synthesised and characterised on the macroscopic scale, with [Pt2(mu-S)2(PPh 3)4Pt(cod)] (BF4)2 and [Pt 2(mu-S)2(PPh3)4Pd(bipy)] (PF 6)2 also characterised by X-ray diffraction studies. No metal scrambling was found to occur, as has been observed in some previous cases involving the related complexes [Pt2(mu-Se)2(PPh 3)4] and [Pt2(mu-S)2(dppe) 2] (dppe=Ph2PCH2CH2PPh2). With cis-[PtCl2(SOMe2)2] the species [Pt 2(mu-S)2(PPh3)4PtCl(SOMe 2)]+ was formed, as a result of the lability of the SOMe2 ligand. With palladium(II)-phosphine systems, the observed product species is dependent on the phosphine; the bulky PPh3 ligand in [PdCl2(PPh3)2] leads primarily to the analogous known species [Pt2(mu-S)2(PPh 3)4PdCl(PPh3)]+, and a small amount of the metal-scrambled species [PtPd2S2(PPh 3)5Cl]+. In contrast, [PdCl2(PTA) 2], containing the small PTA ligand gave [Pt2(mu-S) 2(PPh3)4Pd(PTA)2]2+.

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