Beneficial influence of nanocarbon on the aryliminopyridylnickel chloride catalyzed ethylene polymerization

A series of 1-aryliminoethylpyridine ligands (L1―L3) was synthesized by condensation of 2-acetylpyridine with 1-aminonaphthalene, 2-aminoanthracene or 1-aminopyrene, respectively. Reaction with nickel dichloride afforded the corresponding nickel (II) chloride complexes (Ni1–Ni3). All compounds were fully characterized and the molecular structures of Ni1 and Ni3 are reported. Upon activation with methylaluminoxane (MAO), all nickel complexes exhibit high activities for ethylene polymerization, producing waxes of low molecular weight and narrow polydispersity. The presence of multi-walled carbon nanotubes (MWCNTs) or few layer graphene (FLG) in the catalytic medium can lead to an increase of productivity associated to a modification of the polymer structure

Synthesis and characterization of 2-(2-benzhydrylnaphthyliminomethyl)pyridylnickel halides: formation of branched polyethylene

A series of 2-(2-benzhydrylnaphthyliminomethyl)pyridine derivatives (L1–L3) was prepared and used to synthesize the corresponding bis-ligated nickel(II) halide complexes (Ni1–Ni6) in good yield. The molecular structures of representative complexes, namely the bromide Ni3 and the chloride complex Ni6, were confirmed by single crystal X-ray diffraction, and revealed a distorted octahedral geometry at nickel. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all nickel complex pre-catalysts exhibited high activities (up to 2.02 × 10⁷ g(PE) mol⁻¹(Ni) h⁻¹) towards ethylene polymerization, producing branched polyethylene of low molecular weight and narrow polydispersity. The influence of the reaction parameters and the nature of the ligands on the catalytic behavior of the title nickel complexes were investigated

Au(i)-mediated N2-elimination from triazaphospholes: a one-pot synthesis of novel N2P2-heterocycles

Novel tosyl- and mesitylsulfonyl-substituted triazaphospholes were synthesized and structurally characterized. In an attempt to prepare the corresponding Au(I)-complexes with stoichiometric amounts of AuCl·S(CH3)2, cyclo-1,3-diphospha(III)-2,4-diazane-AuCl-complexes were obtained instead. Our here presented results offer a new strategy for preparing such coordination compounds selectively in a one-pot approach

2-(1-(2-Benzhydrylnaphthylimino)ethyl)pyridylnickel halides: Synthesis, characterization, and ethylene polymerization behavior

A series of 2-(1-(2-benzhydrylnaphthylimino)ethyl)pyridine derivatives (L1–L3) was synthesized and fully characterized. The organic compounds acted as bi-dentate ligands on reacting with nickel halides to afford two kinds of nickel complexes, either mononuclear bis-ligated L₂NiBr₂ (Ni1–Ni3) or chloro-bridged dinuclear L₂Ni₂Cl₄ (Ni4–Ni6) complexes. The nickel complexes were fully characterized, and the single crystal X-ray diffraction revealed for Ni2, a distorted square pyramidal geometry at nickel comprising four nitrogens of two ligands and one bromide; whereas for Ni4, a centrosymmetric dimer possessing a distorted octahedral geometry at nickel was formed by two nitrogens of one ligand, two bridging chlorides and one terminal chloride along with oxygen from methanol (solvent). When activated with diethylaluminium chloride (Et₂AlCl), all nickel complexes performed with high activities (up to 1.22 × 10⁷ g (PE) mol⁻¹(Ni) h⁻¹) towards ethylene polymerization; the obtained polyethylene possessed high branching, low molecular weight and narrow polydispersity, suggestive of a single-site active species. The effect of the polymerization parameters, including the nature of the ligands/halides on the catalytic performance is discussed

The mHz quasi-regular modulations of 4U 1630--47 during its 1998 outburst

We present the results of a detailed timing and spectral analysis of the quasi-regular modulation (QRM) phenomenon in the black hole X-ray binary 4U 1630--47 during its 1998 outburst observed by Rossi X-ray Timing Explore (RXTE). We find that the $\sim$ 50-110 mHz QRM is flux dependent, and the QRM is detected with simultaneous low frequency quasi-periodic oscillations (LFQPOs). According to the behavior of the power density spectrum, we divide the observations into four groups. In the first group, namely behavior A, LFQPOs are detected, but no mHz QRM. The second group, namely behavior B, a QRM with frequency above $\sim$ 88 mHz is detected and the $\sim$ 5 Hz and $\sim$ 7 Hz LFQPOs are almost overlapping. In the third group, namely behavior C, the QRM frequency below $\sim$ 88 mHz is detected and the LFQPOs are significantly separated. In the forth group, namely behavior D, neither QRM nor LFQPOs are detected. We study the energy-dependence of the fractional rms, centroid frequency, and phase-lag of QRM and LFQPOs for behavior B and C. We then study the evolution of QRM and find that the frequency of QRM increases with hardness, while its rms decreases with hardness. We also analyze the spectra of each observation, and find that the QRM rms of behavior B has a positive correlation with $\rm F_{\rm powerlaw}$ / $\rm F_{\rm total}$. Finally, we give our understanding for this mHz QRM phenomena.Comment: 14pages, 15 figure

Highly flexible phosphabenzenes: a missing coordination mode of 2,4,6-triaryl-λ3-phosphinines

The reaction of 2,4,6-triaryl-λ3-phosphinine-Cr(CO)3-π-complexes with [Rh(COD)2]BF4 leads to unusual diamagnetic Rh0-dimers, which contain two phosphinine-π-complexes acting as a bridging 2e−-ligand towards the Rh2(CO)2 core. These compounds represent a missing coordination mode for the aromatic 6-membered phosphorus heterocycle

Bisimino-functionalized dibenzo[a,c]acridines as highly conjugated pincer frameworks for palladium(II): synthesis, characterization and catalytic performance in Heck coupling

A new pair of highly conjugated ligands, 10-[1-(arylimino)ethyl]-14-[(arylimino)methyl]dibenzo[a,c]acridine (aryl = 2,6-Me₂Ph L1, 2,6-Et₂Ph L2) incorporating both aldimine and ketimine units, have been prepared by a straightforward sequence of organic transformations from phenanthrene-9,10-dione. Cyclopalladation occurs readily at ambient temperature on treating L1 or L2 with PdCl₂(NCCH₃)₂ in aprotic solvents to afford exclusively (NketimineNC)Pd(II) chloride pincer complexes Pd1 or Pd2, respectively. By contrast in methanol, Pd1 or Pd2 are isolated as the minor product with aldehyde-containing Pd3 or Pd4 as the major one, the result of hydrolysis of the pendant aldimine units in Pd1 and Pd2, respectively. All the ligands and palladium complexes have been characterized by FT-IR, ¹H and ¹³C NMR spectroscopy, mass spectrometry and elemental analysis; the molecular structures for L1, Pd1, Pd2, Pd3 and Pd4 are also reported. Using low catalyst loadings (0.0005–0.002 mol%) and elevated temperatures (140–200 °C), Pd1–Pd4 are able to efficiently mediate the coupling of haloarenes with vinyl-containing substrates with turnover numbers as high as 174000; the effects of steric/electronic variation within the substrate and NNC-pincer complex on catalyst performance are examined

Ultra-high molecular weight elastomeric polyethylene using an electronically and sterically enhanced nickel catalyst

A collection of ten related 1,2-bis(imino)acenaphthene-nickel(II) halide complexes, [1-[2,6-{(C6H5)2CH}2-4-{C(CH3)3}-C6H2N]-2-(ArN)C2C10H6]NiX2 (X = Br: Ar = 2,6-Me2C6H3Ni1, 2,6-Et2C6H3Ni2, 2,6-iPr2C6H3Ni3, 2,4,6-Me3C6H2Ni4, 2,6-Et2-4-MeC6H2Ni5) and (X = Cl: Ar = 2,6-Me2C6H3Ni6, 2,6-Et2C6H3Ni7, 2,6-iPr2C6H3Ni8, 2,4,6-Me3C6H2Ni9, 2,6-Et2-4-MeC6H2Ni10), each bearing one sterically and electronically enhanced N-2,6-dibenzhydryl-4-t-butylphenyl group, have been prepared and fully characterized. The unsymmetrical nature of the chelating bis(imino)acenaphthene is confirmed in the paramagnetic 1H NMR spectra for Ni1–Ni10, while the molecular structures of Ni1, Ni2 and Ni6 highlight the unequal steric protection of the nickel center imposed by their respective N,N-ligands. On activation with either Et2AlCl or MMAO, all the nickel complexes were highly active catalysts in ethylene polymerization [as high as 1.26 × 107 g of PE per mol of Ni per h] affording exceptionally high molecular weight (up to 3.1 × 106 g mol−1) hyper-branched polyethylene. Analysis of the mechanical properties reveals the ultra-high molecular weight polymers possess high tensile strength, excellent shape fixity and elastic recovery (up to 69%) as well as high elongation at break (εb = 843.9%); such materials offer a promising alternative to current thermoplastic elastomers (TPEs)