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A series of poly-salen type Ni(II) and Co(II) complexes were prepared, and the catalytic behavior in the dimerization of propylene has been studied in combination with aluminum co-catalysts and phosphine ligands. The effects of various reaction factors, such as the type of phosphine ligand and the P/Ni ratio, the type of aluminum co-catalyst and its quantity, particularly the nature of the nickel and cobalt complexes, were also examined. The results indicated that the productivity of the catalytic system was strongly dependent on the steric character of poly-salen ligand in the Ni(II) and Co(II) complexes. It was also found that reaction temperature deeply affected the performance of the catalytic system in the presence of phosphine ligand and alkyl aluminum promoter, and higher regioselectivities to 2,3-dimethylbutenes (2,3DMB) in the dimers were observed with incorporation of bulky and basic PCy3 into the nickel and cobalt catalysts. An extremely high activity in the propylene dimerization (TOF up to 221,000 h-1) was obtained with the 2b system under suitable conditions, which was much higher than that obtained with the corresponding monomeric salen system. However, it seemed difficult to realize recycling of the catalysts owing to the restrict dependence of catalytic activity with its solubility, at least under the adopted conditions.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A novel application of [DTBNpP] Pd(crotyl)Cl (DTBNpP = di-tert-butylneopentylphosphine) (P2), an air-stable, commercially available palladium precatalyst that allows rapid access to a monoligated state, has been identified for room-temperature, copper-free Sonogashira couplings of challenging aryl bromides and alkynes. The mild reaction conditions with TMP in dimethyl sulfoxide afford up to 97% yields, excellent functional group tolerability, and broad reaction compatibility with access to one-pot indole formation.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The anticancer potential of sixteen platinum(ii) complexes with general formulae [PtCl(hq)(S-dmso)] (1a-8a) and [PtCl(hq)(pta)] (1b-8b) (where hq is 5-chloro-7-iodo-8-quinolinol (clioquinol; cqH) (1a, 1b), 8-hydroxy-5-nitroquinoline (nitroxoline; nxH) (2a, 2b), 5,7-dichloro-8-quinolinol (3a, 3b), 5,7-diiodo-8-quinolinol (4a, 4b), 5,7-dibromo-8-quinolinol (5a, 5b), 5,7-dichloro-8-hydroxy-2-methyl-quinoline (6a, 6b), 8-hydroxyquinoline (7a, 7b) and 8-quinolinethiol (8a, 8b); dmso is dimethyl sulfoxide and pta is 1,3,5-triaza-7-phosphaadamantane) was determined through in vitro cytotoxicity assay in human fibroblasts (MRC5) and two carcinoma cell lines (A375 and A549) and embryotoxicity assay in a zebrafish model. Interactions with double stranded DNA through in vitro assay and a molecular docking study were examined. All complexes, except 6a, exhibited a high cytotoxic effect on MRC5 cells at a concentration of 10 mug mL-1 while 1b, 5a, 6a and 3b showed selective toxicity towards carcinoma cell lines. In general, pta-based complexes (series b) were more toxic according to the results of a MTT screen and the LC50 values obtained in zebrafish (Danio rerio) assay; they also induced higher oxidative stress in this model. Successful cellular uptake of complexes was shown by the ICP-MS methodology. The binding propensity of the complex with DNA obtained in in silico studies can be correlated with those from the experimental investigation. Compounds with the highest binding potential, according to the interaction energy value, were 1b, 3b, 6b and 5b. From observations of the DNA interaction ability and of the in silico assessment, no apparent DNA fragmentation was observed either on DNA extracted from the treated cancer cell line or from the zebrafish embryos.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Nickel-catalyzed C-H bond activation has attracted significant attention for the construction of C-C bond frameworks. We report density functional theory investigations into the mechanism of nickel-catalyzed alkylation of benzamides with alkyl halides. Both the Ni(i)-Ni(iii) and Ni(ii)-Ni(iv) catalytic cycles were considered. The theoretical study indicated that the most feasible mechanism involved a Ni(ii)-Ni(iv) catalytic cycle with four main steps: (i) N-H bond activation and (ii) C-H bond activation through the concerted metalation-deprotonation pathway, (iii) oxidative addition of BuBr to give a high-valent Ni(iv) complex, and (iv) C-C reductive elimination to generate the product and the active catalyst. The rate-determining step of the favored pathway is the oxidative addition, leading to the generation of a Ni(iv) intermediate. In addition, the present study casts light on the role of PPh3, which accelerates the cleavage of N-H bond. Frontier molecular orbital theory and natural population analysis were employed to explain the effect of the phosphine ligand on the structure of the Ni complex.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The trans bromide of 2,2-dibromo-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene (Mes*P=CBr2; Mes=2,4,6-tBu3C6H2) can be successfully substituted with an aryl group by using a palladium version of the Kumada-Tamao-Corriu cross-coupling process. Predominant formation of the 2-aryl-2-bromo-1-phosphaethene [(Z)-Mes*P=C(Br)Ar] required suitable conditions including optimization of the ancillary phosphine ligand, thereby retarding the dual elimination of bromides leading to phosphaalkyne (Mes*C?P). The 2-aryl-2-bromo-1-phosphaethenes hold promise as versatile synthons for functional pi-conjugated molecules, and stereospecific transformations of the bromine atom by halogen-metal exchange and palladium-catalyzed arylations were demonstrated.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Development of living polymerizations via reversible activation of dormant species opened the door to discovery of metal-catalyzed living radical polymerization that is now very useful for precise construction of tailor-made polymeric architectures. In this commemorative Perspective, the historical aspects as well as the prospects as a new polymerization tool are described toward advanced structural control or technological materials innovation in various fields.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Rh(i)-Catalyzed decarbonylative direct C-H bond vinylation and dienylation of arenes with readily available acrylic acid and (E)-penta-2,4-dienoic acid under chelation assistance have been developed for the first time. A significant effect of the ligand on the reactivity was observed with the bidentate phosphine ligand being optimal. This protocol was efficient under oxidant-free conditions to access synthetically valuable styrenes and 1-aryl-1,3-butadienes in high yields with a broad substrate scope and good functionality tolerance.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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This review is concerned with data on the composition and structure of intermediate paramagnetic cobalt and nickel compounds in Ziegler-type metal complex catalysts. The problem of reactivity of the intermediate compounds is briefly outlined. General regularities are revealed for the mechanism of formation of the metal complex catalysts. Particular emphasis is made on the structure of intermediates whose EPR spectra explicitly exhibit the effects of vibronic interactions. Vibronic effects are shown to play an important role in the realization of geometric configuration for structures with the pseudodegenerate electronic state. (C) 2000 Elsevier Science B.V.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The efficient and stereoselective synthesis of, or precursors to, multi-substituted alkenes has attracted substantial interest due to their existence in various industrially and biologically important compounds. One of the most atom economical routes to such alkenes is the transition metal catalyzed hetero element?element? pi-insertion into alkynes. This article provides a thorough up-to-date review on this area of chemistry, including discussions on the mechanism, range of E[sbnd]E? bonds accessible and the stoichiometric/catalytic transition metal mediators employed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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An Au-Cu bimetallic nanocluster co-capped by selenolate and phosphine is obtained and its X-ray structure shows an icosahedral Au13 kernel surrounded by three CuSe2PPh2Py motifs and one CuSe3 motif, formulated as [Au13Cu4(PPh2Py)3(SePh)9]. Interestingly, a single-ligand exchange process is observed in the growth reaction, in which an [Au13Cu4(PPh2Py)4(SePh)8]+ intermediate is first formed, but a prolonged reaction leads to one PPh2Py ligand being selectively replaced by a PhSe-ligand. DFT simulations reveal that both steric hindrance and bond dissociation energy have great effects on the single-ligand exchange reaction as well as the thermodynamics, which help to understand the mechanism of the ligand exchange. Temperature-dependent UV-vis absorption and photoluminescence (PL) properties of the Au-Cu nanocluster imply that the optical properties are mainly contributed by the metal core. Femtosecond time-resolved pump-probe analysis maps out further details of the PL process.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate