Titanium complexes bearing aromatic-substituted β-enaminoketonato ligands: Syntheses, structure and olefin polymerization behavior

A series of titanium complexes [(Ar)NC(CF₃)CHC(R)O]₂TiCl₂ (4b: Ar = -C₆H₄OMe(p), R = Ph; 4c: Ar = -C₆H₄Me(p), R = Ph; 4d: Ar = -C₆H₄Me(o), R = Ph; 4e: Ar = α-Naphthyl, R = Ph; 4f: Ar = -C₆H₅, R = t-Bu; 4g: Ar = -C₆H₄OMe(p); R = t-Bu; 4h: Ar = -C₆H₄Me(p); R = t-Bu; 4i: Ar = -C₆H₄Me(o); R = t-Bu) has been synthesized and characterized. X-ray crystal structures reveal that complexes 4b, 4c and 4h adopt distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4b-c and 4f-i are active catalysts for ethylene polymerization and ethylene/norbornene copolymerization, and produce high molecular weight polyethylenes and ethylene/norbornene alternating copolymers. In addition, the complex 4c/MMAO catalyst system exhibits the characteristics of a quasi-living copolymerization of ethylene and norbornene with narrow molecular weight distribution.     

N‐Silylaminotitanium Chlorides — Synthesis,Structures, Multinuclear Magnetic Resonance,and some Applications

N‐Silylaminotitanium trichlorides, Me₃S(R)N‐TiCl₃ ( 18 ) [R = ^tBu ( a ), SiMe₃ ( b ), 9‐borabicyclo[3.3.1]nonyl (9‐BBN)( c )], and (CH₂SiMe₂)₂N‐TiCl₃ ( 18d ) were obtained in high yield and high purity from the reaction of the respective bis(silylamino)plumbylene with an excess of titanium tetrachloride. The crystal structure of 18a was determined by X‐ray analysis. The reactions of the analogous stannylenes with an excess of TiCl₄ did not lead to 18 . N‐Lithio‐trimethylsilyl[9‐(9‐borabicyclo[3.3.1]nonyl)]amine ( 8 ) was prepared, structurally characterized and used for the synthesis of a new bis(amino)stannylene 10 and a plumbylene 11 . The compounds 18a—d served as ideal starting materials for the synthesis of bis(silylamino)titanium dichlorides, where the silylamino groups can be identical ( 19 ) or different ( 20 ). This was achieved either by the reaction of 18 again with bis(amino)plumbylenes or with lithium N‐silylamides. In contrast to the direct synthesis starting from titanium tetrachloride and two equivalents of the respective lithium amide, which in general affords 19 with identical amino groups only in low yield, the procedure starting from 18 is much more versatile and gave the pure compounds 19 or 20 in almost quantitative yield. Further treatment of the dichlorides 19 or 20 with lithium amides led to tris(amino)titanium chlorides 21 . The dichlorides 19 or 20 reacted with two equivalents of alkynyllithium reagents to give the first well characterized examples of di(alkyn‐1‐yl)bis(N‐silylamino)titanium compounds 22 — 27 . These compounds reacted with trialkylboranes (triethyl or tripropylborane) by 1, 1‐organoboration. In some cases, the extremely reactive reaction products could be identified as novel 1, 1‐bis(silylamino)titana‐2, 4‐cyclopentadienes 28 — 31 bearing a dialkylboryl group in 3‐position. In solution, the proposed structures of all products were deduced from a consistent set of data derived from multinuclear magnetic resonance spectroscopy (¹H, ¹¹B, ¹³C, ¹⁴N, ¹⁵N, ²⁹Si, ³⁵Cl NMR).     

Mild and Efficient Deoxygenation of Amine-N-oxides with Titanium Tetrachloride-Indium System

Abstract

TiCl₄/In system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.     

Conduction mechanism of metal-TiO2–Si structures

The conduction model has been proposed for the metal-TiO₂–Si (MIS) structures. Rutile films have been prepared on Si substrates by magnetron sputtering of TiO₂ target and annealing in the air at temperatures T?=?800 and 1050 K. The current-voltage (CVC) and capacitance-voltage characteristics of the structures have been measured over the range of T?=?283–363 K. At positive potentials on the gate, the conductivity of the MIS structures is determined by the space charge-limited current in the dielectric layer.     

Exploration of silver decoration concentration to enhance photocatalytic efficiency of titanium dioxide photocatalysts

Ag decoration on TiO₂ is favorable to absorption of visible light and wider absorption range. Ag nanoparticles playing the role of electron receivers on TiO₂ surface enhance photodegradation. However, excess Ag nanoparticles caused reduced specific surface area of photocatalysts and increased probability of charge recombination, resulting in lower photocatalytic efficiency. In this study, the influence of various Ag decoration concentrations on photocatalytic activity was investigated. Surface treatment by nitric acid after Ag decoration was performed to avoid excessive Ag deposition. The extent of Ag elimination and its impacts on photocatalytic activity were also explored. An optimum Ag content in the photocatalyst was achieved and photocatalytic efficiency was obviously improved. It was found that the number of calcination times affected the crystallinity and stability of photocatalysts. Better photocatalytic efficiency could be obtained after twice calcinations.     

NIEDERKOORDINIERTE PHOSPHORVERBINDUNGEN, 701 1-METALLA-2,5-DIPHOSPHA PENTA-1,3-DIENE DURCH 1,4-ADDITION VON METALLCARBONYLCYCLOPENTADIENYLHYDRIDEN AN 1,4-DIPHOSPHABUTA-1,3-DIEN

Abstract

Reactions of carbonyl cyclopentadienyl hydrides from molybdenum and tungsten with 1,4-diphosphabuta-1,3-diene yield metalla-diphospha-pentadiene with a metal-phosphorus-double bond.

Metalla-diphosphapentadiene mit einer Metall-Phosphor-Doppelbindung werden durch Umsetzung von Carbonylcyclopentadienylhydriden des Molybdäns und Wolframs mit einem 1,4-Diphospha-buta-1,3-dien erhalten.     

A potential flower-like coating consisting of calcium-phosphate nanosheets on titanium surface

A potential calcium-phosphate fl ower-like nanocoating were coated onto the titanium surface in an easy approach. It has high surface area, low cytotoxicity as well as promising cell affi nity, which makes it a potential alternative modifi cation method for titanium surface.     

Dynamics of water adsorption on TiO2 monitored by work function spectroscopy

Water adsorption dynamics on two TiO₂ (1 1 0) rutile surfaces at room temperature has been investigated using the work function (WF) change as a function of time. The first surface was prepared in a standard way using sputtering/annealing cycles, whereas the second one was long term annealed at 620 K in moderate vacuum conditions (the residual gas pressure of about 1 × 10⁻⁷ mbar) and cleaned afterwards. The WF change show striking difference as compared to those obtained for highly reduced TiO₂ (1 1 0) rutile or the (2 × 1) reconstructed surfaces. For the first kind of surface we show that the observed adsorption dynamics can be qualitatively explained by the present understanding of the water adsorption on non-reconstructed TiO₂ (1 1 0) rutile surface according to which the bridging oxygen vacancies and Ti rows are the main adsorption sites. Although generally similar to the former results, water adsorption dynamics on the second kind of the surface has an additional feature that can be only explained by a new adsorption site, which we suggest to be due to (2 × 1) reconstructed regions coexisting with the non-reconstructed TiO₂ (1 1 0) surface.     

Study on the Structure of TiO2 Thin Film by Means of Diffuse Reflectance Infrared Fourier Transform Spectroscopy

The diffuse reflectance infrared spectra of TiO₂ thin films deposited on different base materials and formed under different experimental conditions(temperature, ratio of tetrabutyl titanate to water and adulteration of different metallic elements) were determined and the structure of the films were discussed.