Molecular nitrides containing group 4 and 5 metals: single and double azatitanocubanes

Treatment of [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) with the imido complexes [Ti(NAr)Cl(2)(py)(3)] (Ar=2,4,6-C(6)H(2)Me(3)) and [Ti(NtBu)Cl(2)(py)(3)] in toluene affords the single azatitanocubanes [[Cl(2)(ArN)Ti]( micro(3)-NH)(3)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (2.C(7)H(8)) and [[Cl(2)Ti](micro(3)-N)(2)(micro(3)-NH)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (3), respectively. Similar reactions of complex 1 with the niobium and tantalum imido derivatives [[M(NtBu)(NHtBu)Cl(2)(NH(2)tBu)](2)] (M=Nb, Ta) in toluene give the single azaheterometallocubanes [[Cl(2)(tBuN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (M=Nb (4), Ta (5)), both complexes react with 2,4,6-trimethylaniline to yield the analogous species [[Cl(2)(ArN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (Ar=2,4,6-C(6)H(2)Me(3), M=Nb (6.C(7)H(8)), Ta (7.C(7)H(8))). Also the azaheterodicubanes [M[micro(3)-N)(2)(micro(3)-NH)](2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2C(7)H(8) [M=Ti (8.2C(7)H(8)), Zr (9.2C(7)H(8))], and [M[(micro(3)-N)(5)(micro(3)-NH)][Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2 C(7)H(8) (Nb (10.2C(7)H(8)), Ta (11.2C(7)H(8))) were prepared from 1 and the homoleptic dimethylamido complex [M(NMe(2))(x)] (x=4, M=Ti, Zr; x=5, M=Nb, Ta) in toluene at 150 degrees C. X-ray crystal structure determinations were performed for 6 and 10, which revealed a cube- and double-cube-type core, respectively. For complexes 2 and 4-7 we observed and studied by DNMR a rotation or trigonal-twist of the organometallic ligands [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) and [(micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]](1-). Density functional theory calculations were carried out on model complexes of 2, 3, and 8 to establish and understand their structures.     

Development of new glass composite membranes and their properties for low temperature H2/O2 fuel cells.

A new glass electrolyte formed by constant amounts of titanium oxide (TiO2) and various amount of phosphotungstic acid (PWA) doped P2O5-SiO2 is prepared using the sol-gel process. The structural formation is confirmed by Fourier infrared spectroscopy (FTIR) and from thermogravimetric and differential thermal analysis (TG/DTA) measurements, the glasses display good thermal stability. Further characterisation is undertaken by N2 adsorption/desorption measurements, proton conductivity and hydrogen permeability analyses and a H2/O2 fuel cell test is also performed. The glass materials with large pores and specific surface area are suitable for use as the electrolyte in H2/O2 fuel cells. The effect of TiO2 processing with constant amount of PWA in phosphosilicate glasses, is investigated and discussed. The hydrogen permeability is 1.57x10(-11) mol cm(-1) s(-1) Pa(-1) at 110 degrees C for 0.8 mm thick glass; a power density of 46.3 mW cm(-2) at 125 mA cm(-2) and a current density of 175 mA cm(-2) is obtained (T=28 degrees C, relative humidity).     

Preparation and application of Ce-doped mesoporous TiO2oxide

Summary Mesoporous TiO₂-CeO₂mixed oxides (m-TiO₂-CeO₂) were synthesized under easy-operating neutral conditions. The structure was characterized by means of FT-IR, XRD, and N₂adsorption methods. For methanol decomposition to CO and H₂, the catalytic activity of the Ru/ m-TiO₂-CeO₂ catalyst was higher than that of the Ru/ m-TiO₂.</o:p>     

二氧化钛纤维表面担载Pt纳米结构的原子力显微镜研究

通过原子力显微镜研究了二氧化钛纤维表面担载Pt的表面形貌及其结构.结果表明,TiO2纤维表面担载的Pt具有微米尺度的近似六边形或者近似长方形的结构,与在单晶TiO2(110)表面的Pt纳米簇形貌相似,但尺度较大.TiO2纤维担载的Pt表面明显存在不同高度的台阶结构,台阶高度以2~4倍Pt(111)晶面面间距的高度为主.由Pt在TiO2纤维表面的形貌与纤维的纳米晶粒排布有序性推测可知,Pt与TiO2纤维存在强的相互作用,可能正是这种强相互作用和表面台阶结构才使TiO2表面担载的Pt虽是微米尺寸但仍具有高光催化活性.     

Syntheses and Crystal Structures of Some CCo3 Clusters Containing PPh3 or dppm Ligands

Molecular structural determinations are reported for six Co₃C carbonyl cluster complexes containing tertiary phosphines, which have been isolated as by-products from a variety of reactions. Structural features are similar to those of related complexes already reported. Some discussion of apparent orientational preferences of the CH₂ group of dppm ligands, which appear to enter into H-bonding interactions with amido or carboxylate substituents, is given. Appropriate comparisons are made with unsubstituted analogues.     

Preparation and characterization of nitrogen-doped titanium dioxides

A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated.     

Silicon Carbide Supported Palladium‐Iridium Bimetallic Catalysts for Efficient Selective Hydrogenation of Cinnamaldehyde

Selective hydrogenation of α,β‐unsaturated carbonyls into saturated carbonyls is important to obtain remunerative products. However, it is still a challenge to achieve high activity and selectivity under mild conditions. Herein, Pd, Ir and bimetallic Pd‐Ir nanoparticles were uniformly deposited with high dispersity on the surface of SiC by a facile impregnation method, respectively. The as‐prepared Pd/SiC catalysts efficiently hydrogenate cinnamaldehyde to hydrocinnamaldehyde at room temperature and atmospheric pressure, and the activity of Pd/SiC is observed further enhanced by adding Ir component (conversion of 100%). In addition, the dependence of Pd‐Ir catalyst activity on Pd/Ir molar ratio confirms a synergistic effect between Ir and Pd, which originates from the electron transfer between Pd and Ir.     

Early-late heterobimetallic alkoxides as model systems for late-transition-metal catalysts supported on titania

Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies.     

Construction of database of effective energy‐loss functions

Effective energy‐loss functions for Al, Cu, Ag and Au were derived from the reflection electron energy‐loss spectroscopy (REELS) spectra for 1 keV electrons using extended Landau theory. Features of the obtained effective energy‐loss functions are close to those of optical surface energy‐loss functions, revealing the significant contribution of the low energy loss below a few tens of electron‐volts in the REELS spectrum for Cu, Ag and Au. The REELS spectra were reproduced using the newly derived effective energy‐loss functions, leading to the confirmation that this type of database of the effective energy‐loss function is very useful not only for more comprehensive understanding of the measured spectrum of surface electron spectroscopies but also for practical background subtraction in surface electron spectroscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

Study of bulk chain coupling reactions. I. Reaction between bisoxazolones and amine-terminated polyamide 12

2,2′-Bis(4,4-dimethyl-5(4H)-oxazolone) ( B3 ) and 2,2′-(1,2-ethylene)-bis(4,4-dimethyl-5(4H)oxazolone) ( B4 ) have been reacted in the bulk with α, ω-diamino polyamide-12 ( PA12 ) of M?_n = 1000. The reactions have been studied by SEC, and ¹H- and ¹³C-NMR and resulting polymers characterized by DSC and TGA. The chain coupling reaction is fast and gives high molar mass polymers within 10 min at 200°C with B4 while some side reactions occur with B3 leading to polymers of lower molar mass. The crystallinity of resulting polymers is lower than that of starting oligomer. However, the thermal stability is higher. Model reactions using B3 or B4 and hexamethylene diamine or 1-dodecanamine have been carried out and studied. An intramolecular cyclodehydration giving 2-imidazolin-5-ones takes place during the reactions. Higher cyclization extent is found in the presence of amino group excess. 2-Imidazolin-5-one heterocyclic structures are also observed in the chains of the polymers obtained from PA12 and B3 or B4 . © 1993 John Wiley & Sons, Inc.