Synthesis, structure and α-olefin polymerization activity of group 4 metal complexes with [OSSO]-type bis(phenolate) ligands

The tetradentate [OSSO]-type bis(phenol) ligands, [{2,2′-(HOC₆H₂-4,6-R₂)₂CH₂SCH₂CH₂SCH₂}] (R = ^tBu, 2; Br, 3) react with MBz₄ (M = Zr, Hf) to yield the corresponding dibenzyl complexes, [M{2,2′-(OC₆H₂-4,6-R₂)₂CH₂SCH₂CH₂SCH₂}Bz₂] (R = Br, M = Zr, 4^Br; Hf, 5^Br; R = ^tBu, M = Hf, 5) in a good to very good yield. Zirconium diamido complexes, [Zr{2,2′-(OC₆H₂-4,6-R₂)₂CH₂SCH₂CH₂SCH₂}(NMe₂)₂] (R = ^tBu, 6; Br, 6^Br) were prepared in a reaction of the corresponding disodium salt of 2 or 3 generated in situ with ZrCl₂(NMe₂)₂(THF)₂. Heating of 6 with TMSCl at 35 °C afforded zirconium dichloro complex, [Zr{2,2′-(OC₆H₂-4,6-^tBu₂)₂CH₂SCH₂CH₂SCH₂}Cl₂] (7), whereas the titanium analog 8 was prepared in a direct reaction with TiCl₄. While for complexes 4^Br, 5, 5^Br, 6, 6^Br and 7 single C₂-symmetric isomers were observed in solution at room temperature, as revealed by the NMR spectroscopic data, titanium complex 8 formed as a mixture of cis-α (8a) and cis-β (8b) isomers in a ratio of approx. 20:80% (measured in CD₂Cl₂). The VT NMR studies revealed a reversible conversion of 8a into 8b above 60 °C. The X-ray crystal structure determination of complexes 4^Br, 5^Br and 7 confirmed their C₂-symmetrical configuration in the solid state with cis-arranged benzyl/chloro groups and the trans-coordination of two bulky phenolato moieties. The zirconium dibenzyl complexes exhibit good catalytic activities in homopolymerization of 1-hexene (atactic poly(1-hexene), PDI = 1.5-1.7) and vinylcyclohexane (isotactic poly(vinylcyclohexane), PDI = 1.2-1.8) upon activation with a co-catalyst. In both polymerizations no increase of activity was observed for the complex 4^Br with electron-withdrawing substituents on phenolate rings. Moreover, polymerization of liquid propylene catalyzed by the titanium dichloro isomeric mixture 8 afforded at 5 °C ultrahigh molecular weight atactic/isotactic polypropylene mixtures.     

Low-temperature phase of Li2FeSiO4: crystal structure and a preliminary study of electrochemical behavior

A nearly single-phase of a low-temperature (LT) phase of Li(2)FeSiO(4) is prepared by a hydrothermal method at 150 °C. We report the detailed crystal structure of LT-Li(2)FeSiO(4) (S.G. Pmn2(1)) by applying Rietveld/MEM analysis to the synchrotron XRD pattern. LT-Li(2)FeSiO(4) shows 150 mA h g(-1) as the positive electrode materials of rechargeable batteries.     

Anion conductive block poly(arylene ether)s: synthesis, properties, and application in alkaline fuel cells

Anion conductive aromatic multiblock copolymers, poly(arylene ether)s containing quaternized ammonio-substituted fluorene groups, were synthesized via block copolycondensation of fluorene-containing (later hydrophilic) oligomers and linear hydrophobic oligomers, chloromethylation, quaternization, and ion-exchange reactions. The ammonio groups were selectively introduced onto the fluorene-containing units. The quaternized multiblock copolymers (QPEs) produced ductile, transparent membranes. A well-controlled multiblock structure was responsible for the developed hydrophobic/hydrophilic phase separation and interconnected ion transporting pathway, as confirmed by scanning transmission electron microscopic (STEM) observation. The ionomer membranes showed considerably higher hydroxide ion conductivities, up to 144 mS/cm at 80 °C, than those of existing anion conductive ionomer membranes. The durabilities of the QPE membranes were evaluated under severe, accelerated-aging conditions, and minor degradation was recognized by (1)H NMR spectra. The QPE membrane retained high conductivity in hot water at 80 °C for 5000 h. A noble metal-free direct hydrazine fuel cell was operated with the QPE membrane at 80 °C. The maximum power density, 297 mW/cm(2), was achieved at a current density of 826 mA/cm(2).     

Aromatic character of polycyclic π systems formed by fusion of two or more rings of the same size

The sequential line plot of topological resonance energy (TRE) against the number of π electrons (N(π)) for any polycyclic aromatic hydrocarbon (PAH) is very similar with the same number of extrema to that for benzene. Thus, global aromaticity of a PAH molecular ion strongly reflects that of a benzene molecular ion. Likewise, the N(π) dependence of TRE for any polycyclic π system formed by fusion of two or more rings of the same size reflects that for a monocyclic species of the same ring size. In general, TREs for such polycyclic π systems and their molecular ions can be interpreted consistently by reference to those for neutral and charged monocyclic species of the same ring size.     

Surfactant-free synthesis of palladium nanoclusters for their use in catalytic cross-coupling reactions

Surfactant-free Pd nanoclusters (Pd NCs) (size: 1-1.5 nm) showed high catalytic activity in the Suzuki-Miyaura cross-coupling and Mizoroki-Heck reactions. The Pd NCs had a high turnover number, up to 6.0 × 10(8), which can be recycled at least five times without loss of catalytic activity.     

Polybenzimidazole block sulfonated poly(arylene ether sulfone) ionomers

Novel ionomers based on polybenzimidazole block sulfonated poly(arylene ether sulfone) show excellent thermal properties. The ionic aggregation of sulfonic acid groups leads to well-developed phase separated morphology and thus high proton conductivity at wide humidity range, up to 65 mS cm(-1) at 90% relative humidity.     

Adjoint-based exact Hessian computation

BIT Numerical Mathematics - We consider a scalar function depending on a numerical solution of an initial value problem, and its second-derivative (Hessian) matrix for the initial value. The need...     

Velocity and metastable state population distributions of neodymium atoms produced by laser ablation

Laser-induced fluorescence spectroscopy has been employed to characterize the plume produced in nanosecond laser ablation of metallic neodymium. The kinetic-energy distributions of the neutral and ionized atoms in the plume under both vacuum and gas environments have been investigated. The population distribution of metastable levels in the ablated atoms was also derived. The results show that some metastable states are more heavily populated than predicted by a Boltzmann-type distribution. These investigations provide preliminary data for the design of a new type of resonance photo-ionization laser ion source as well as for high-resolution laser spectroscopy of refractory elements. PACS 52.38.Mf; 33.50.Dq; 42.62.Fi     

Synthesis and properties of polyimide ionomers containing sulfoalkoxy and fluorenyl groups

A series of sulfopropylated and sulfobutylated polyimide copolymers containing fluorenyl groups, SPI‐4, were synthesized to investigate the effect of alkyl side chains on the properties (stability, mechanical strength, water uptake, and proton conductivity) of the polymimide electrolyte membranes. SPI‐4 showed much better hydrolytic stability (in 10% MeOH aq at 100 °C) than the main chain sulfonated polyimide, SPI‐1. Tough, flexible, and ductile membranes were obtained from these copolymers. At high relative humidity all the SPI‐4 membranes showed high mechanical properties (>34 MPa of the maximum stress) and proton conductivity (>0.1 Scm^?1). These properties are comparable to or even better than those of the perfluorosulfonic acid ionomer (Nafion 112). The new polyimide ionomers have proved to be a possible candidate as polymer electrolyte membrane for PEFCs and DMFCs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4439–4445, 2005