Experimental and theoretical molecular and electronic structures of the N-oxides of pyridazine,pyrimidine and pyrazine

The structures of pyridazine N-oxide, pyrimidine N-oxide and pyrazine N-oxide have been determined by X-ray diffraction for the first time. Comparison with theoretical predictions of the equilibrium structures using the B3LYP method together with a cc-pVTZ basis set, show close agreement with the structural parameters observed, and experimental dipole moments, which suggests that the charge distribution is realistic. An ‘atoms in molecules’ (AIM) analysis of the computed wave-functions shows total electron densities rather different from the classical picture of a dative bond, whereas the same wave-functions subjected to Mulliken analysis show a more conventional view of the electron distribution. This latter procedure allows a bond dipole analysis of the N-oxide charge distribution.     

On the Development of Titanium κ1-Amidinate Complexes,Commercialized as Keltan ACE™ Technology,Enabling the Production of an Unprecedented Large Variety of EPDM Polymer Structures

ARLANXEO Elastomers has developed and commercialized Keltan ACE™ technology, a class of half-sandwich cyclopentadienyl κ¹-amidinate metal complexes, which are extremely active for the production of first-class ethylene/propylene/diene copolymers (EPDM). In this review, the development and some of the key features of the Keltan ACE™ catalyst system are presented. Many different ACE catalysts have been synthesized over the past years, including bridged and bimetallic catalysts. With Keltan ACE™, a complete range of EPDM products with similar polymer characteristics as their Ziegler–Natta (ZN) counterparts can be produced, including variations containing very high 5-ethylidene-2-norbornene (ENB) contents, controlled long chain branching, very high molecular weight, as well as oil-extended products. Moreover, other EPDM structures can be polymerized. The Keltan ACE™ catalyst technology also allows the production of EPDMs with very high amounts of dicyclopentadiene (DCPD) or 5-vinyl 2-norbornene (VNB) without excessive gelation and reactor fouling, that is, products that cannot or are extremely difficult to obtain via classical ZN catalysis. In a next step, high-VNB-EPDM can be postreactor modified, for example, via metathesis chemistry. In addition, EPDM polymers with a very broad or even bimodal molecular weight distribution can be obtained in a single reactor with certain ACE catalyst structures at particular activator/precatalyst ratios. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2877–2891     

Evidence of an equilibrium between selenides and osmium(VIII) reagents and selenoxides and osmium(VI) reagents

Driving the equilibrium between selenides and osmium(VIII) reagents with selenoxides and osmium(VI) by a subsequent reaction (rearrangement of allyl selenoxides to allyl alcohols or addition of osmium(VIII) species on C=C double bonds) to one side, allows the transformation of methyl geranyl selenides to linalool and of methyl citronellyl selenoxide to 6,7-dihydroxy citronellyl selenide.     

Polyferrocenylsilane microspheres: synthesis,mechanism of formation,size and charge tunability,electrostatic self-assembly,and pyrolysis to spherical magnetic ceramic particles

Pt(0)-catalyzed ring-opening precipitation copolymerization of [1]silaferrocenophanes fcSiMe(2) (3) and the spirocyclic cross-linker fcSi(CH(2))(3) (4) (fc = Fe(eta(5)-C(5)H(4))(2)) was used to prepare polyferrocenylsilane microspheres (PFSMSs) under mild conditions. By varying the reaction conditions, a wide variety of other morphologies was obtained. The effects of temperature, monomer ratio, solvent composition, catalyst concentration, and time on the observed morphology were investigated and interpreted in terms of a mechanism for microsphere formation. The most well-defined particles were formed using equimolar amounts of 3 and 4, in a 50:50 mixture of xylenes and decane at 60 degrees C with gentle agitation. Chemical oxidation of the polymeric microspheres led to positively charged particles (OPFSMSs) which underwent electrostatically driven self-assembly with negatively charged silica microspheres to form core-corona composite particles. Redox titration with controlled amounts of the one-electron oxidant [N(C(6)H(4)Br-p)(3)][PF(6)] in acetonitrile led to the oxidation of the outer 0.15 microm (ca. 32%) of the PFSMSs. The resulting OPFSMSs were reduced back to their neutral form by reaction with hydrazine in methanol. Pyrolysis of the PFSMSs led to spherical magnetic ceramic replicas with tunable magnetic properties that organize into ordered 2-D arrays at the air-water interface under the influence of a magnetic field.     

Characterization of laser-ablated and chemically reduced silver colloids in aqueous solution by UV/VIS spectroscopy and STM/SEM microscopy

Silver colloids in aqueous solution were studied by different scanning microscopy techniques and UV/VIS spectroscopy. The silver colloids were produced either by chemical reduction or by nanosecond laser ablation from a solid silver foil in water. Variation of laser power and ablation time leads to solutions of metal clusters of different sizes in water. We characterized the electronic absorption of the clusters by UV/VIS spectroscopy. STM (scanning tunneling microscope) imaging of the metal colloids shows atomic resolution of rod- or tenon-like silver clusters up to 10-nm length formed by laser ablation. Our scanning electron microscope measurements, however, show that much larger silver colloids up to 5-μm length are also formed, which are not visible in the STM due to their roughness. We correlate them with the long-wavelength tail of the multimodal UV/VIS spectrum. The silver colloids obtained by chemical reduction are generally larger and their electronic spectra are red-shifted compared to the laser-ablated clusters. Irradiation of the colloid solution with nanosecond laser pulses of appropriate fluence at 532 nm and 355 nm initially reduced the colloid size. Longer irradiation at 355 nm, however, leads to the formation of larger colloids again. There seems to be a critical lower particle size, where silver clusters in aqueous solution become unstable and start to coagulate. Received: 24 June 2002 / Revised version: 25 July 2002 / Published online: 25 October 2002 RID="*" ID="*"This work is part of the thesis of H. M?ltgen RID="**" ID="**"Corresponding author. Fax: +49-211/811-5195, E-mail: kleinermanns@uni-duesseldorf.de