Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes

Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe(2)R')(Pyr)(2)(bipy) (1a-1g; R = 2,6-i-Pr(2)C(6)H(3) (Ar), adamantyl (Ad), 2,6-Me(2)C(6)H(3) (Ar'), 2-i-PrC(6)H(4) (Ar(iPr)), 2-ClC(6)H(4) (Ar(Cl)), 2-t-BuC(6)H(4) (Ar(t) (Bu)), and 2-MesitylC(6)H(4) (Ar(M)), respectively; R' = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans and two possible cis pyrrolide isomers of syn alkylidenes. Sonication of a mixture containing 1a-1g, HMTOH (2,6-dimesitylphenol), and ZnCl(2)(dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe(2)R')(Pyr)(OHMT) (3a-3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a-3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to formation of imido alkylidyne complexes of the type Mo(NR)(CCMe(2)R')(Me(2)Pyr)(bipy) (Me(2)Pyr = 2,5-dimethylpyrrolide; 4a - 4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe(2)Ph)(Pyr)(2)(bipy) (1a), Mo(NAr(iPr))(CHCMe(2)Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe(2)Ph)(Me(2)Pyr)(bipy) (4a), and Mo(NAr(T))(CCMe(3))(Me(2)Pyr)(bipy) (Ar(T) = 2-(2,4,6-i-Pr(3)C(6)H(2))C(6)H(4); 4g) showed structures with the normal bond lengths and angles.     

P-N bond length alterations monitored by infrared absorption and Fourier transform Raman spectroscopy in combination with density functional theory calculations

Fourier transform (FT) Raman and infrared spectroscopy in combination with density functional theory calculations have been applied to the vibrational characterization of the dimeric zinc diphenylphosphanyl(trimethylsilyl)amide complex [(Me3Si)2NZnPh2PNSiMe3]2 and the ortho-metallated species [Li(o-C6H4PPh2NSiMe3)]2 x Et2O in relation to their parent starting materials diphenylphosphanyl (trimethylsilyl)amine Ph2P-N(H)SiMe3 and iminophosphorane Ph3P=NSiMe3. The spectroscopic changes evidenced in the spectra were correlated with the structural parameters in order to provide insight as to what extent the P-N bond is affected by the coordination to the metal center. The employment of density functional theory (DFT) calculations in addition to these spectroscopic methods offers the possibility of predicting whether the Lewis-basic imido nitrogen atom is involved in coordination not only in the solid state, but also in the gas phase.     

Molybdenum Imido Alkylidene Metathesis Catalysts that Contain Electron Withdrawing Biphenolates or Binaphtholates

We have prepared new Mo(NR)(CHCMe(2)Ph)(diolate) complexes (R = 2,6-i-Pr(2)C(6)H(3), 2,6-Me(2)C(6)H(3), 1-Adamantyl, or 2-CF(3)C(6)H(4)) that contain relatively electron-withdrawing binaphtholate (3,3'-bis-(9-anthracenyl), 3,3'-bispentafluorophenyl, or 3,3'-bis(3,5-bis(trifluoromethyl)phenyl) or biphenolate (3,3'-di-tert-butyl-5,5'-bistrifluoromethyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diolate) ligands. We also have prepared new monomeric Mo(NR)(CHCMe(2)Ph)(2,5-dimethylpyrrolide)(2) complexes and have treated them with biphenols or binaphthols in order to prepare several Mo(NR)(CHCMe(2)Ph)(diolate) species. In one case the new Mo(NR)(CHCMe(2)Ph)(diolate) complexes could be prepared only through reaction of a binaphthol [3,3'-bis(pentafluorophenyl)binaphthol] with a bis(2,5-dimethylpyrrolide) complex. The pyrrolide approach can be employed either to isolate catalysts on a preparative scale or to generate catalysts in situ. Several simple preliminary ring-closing metathesis reactions show that the new complexes are catalytically competent.     

Borane B-C Bond Cleavage by a Low-Coordinate Iron Hydride Complex and N-N Bond Cleavage by the Hydridoborate Product

The iron(II) hydride dimers [L(R)Fe(μ-H)(2)FeL(R)] (L(Me) = 2,4-bis(2,6-diisopropylphenylimino) pent-3-yl; L(tBu) = 2,2,6,6-tetramethyl-3,5-bis(2,6-diisopropylphenylimino)hept-4-yl) abstract hydrocarbyl groups from BR'(3) (R' = Et, Ph) to give L(R)FeR' and L(R)Fe(μ-H)(2)BR'(2). Mechanistic studies with R = R' = Me are consistent with a process in which the hyride dimer opens one Fe-H bond, and subsequent B-H bond formation is concerted with dissociation of an Fe-H unit. Cleavage of boron-carbon bonds is likely to proceed at least in part from transient quaternary borate anions. In a separate bond-breaking reaction, L(Me)Fe(μ-H)(2)BEt(2) reacts with N(2)H(4) to eject H(2) from the bridging hydrides and cleave the N-N bond in the diaminoborate complex L(Me)Fe(μ-NH(2))(2)BEt(2). These novel bond-breaking reactions are facilitated by the low coordination number at the iron(II) center.     

Catalytic reduction of dinitrogen to ammonia at well-defined single metal sites

Dinitrogen (N2) is reduced to ammonia at room temperature and 1atm with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands {[HIPTN3N]3-=[{3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2}3N]3-, an example being [HIPTN3N]Mo(N2)} in heptane. Slow addition of the proton source ({2,6-lutidinium}{BAr'4}; Ar'=3,5-(CF3)2C6H3) and reductant (decamethyl chromocene) assure a high yield of ammonia (63-65% in four turnovers) versus dihydrogen formation. Numerous X-ray studies, along with isolation and characterization of seven intermediates in the proposed catalytic reaction (under noncatalytic conditions), suggest that N2 is being reduced at a sterically protected, single Mo centre that cycles between states Mo(III), Mo(IV), Mo(V) and Mo(VI).     

Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp(2)Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible beta-hydrogens undergo insertion/protonation of the C-X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible beta-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations support a stepwise pathway with zwitterionic intermediates for the first reaction class and a concerted pathway for the second reaction class. Additionally, the feasibility of chirality transfer from the planar-chiral ebthi (ebthi = ethylenebis(tetrahydroindenyl)) ligand was demonstrated with a chiral analogue, (ebthi)-Zr=NAr(THF) (Ar = 2,6-dimethylphenyl), 2, through the diastereoselective ring opening of meso epoxides.     

Synthesis, Characterization, and Reactions of Isolable (β-Diketiminato)Nb(III) Imido Complexes

We have investigated both the chemical reduction of (BDI)Nb(V) imido complexes (BDI = HC[C(Me)NAr](2); Ar = 2,6-(i)Pr(2)-C(6)H(3)) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, the novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(N(t)Bu)(NAr)(L') (L' = py, thf) were formed by either KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) in the absence of strong π-acids or by H(2) reduction of the Nb(V) dimethyl complex (BDI)Nb(N(t)Bu)Me(2) in THF. These products are likely formed though an intramolecular, 2 e(-) reductive C-N bond cleavage, as has been observed previously for related Group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(N(t)Bu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (A(iso){(93)Nb} = 120.5×10(-4) cm(-1), A(iso){(31)P} = 31.0×10(-4) cm(-1), g(iso) = 1.9815). When strong π-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(N(t)Bu)(py) prior to reductive cleavage of the ligand C-N bond, the thermally stable Nb(III) species (BDI)Nb(N(t)Bu)(CX)(2)(L″) (X = O, L″ = py; X = NXyl, L″ = CNXyl; Xyl = 2,6-Me(2)-C(6)H(3)) were obtained in good yields. The Nb(III) complexes (BDI)Nb(N(t)Bu)py, (BDI)Nb(N(t)Bu)(CO)(2)(py) and (BDI)Nb(N(t)Bu)(CO)(2) were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal-ligand multiple bond formation and for the reduction of organic π-systems. The reduction of mesityl azide by (BDI)Nb(N(t)Bu)(py) and diphenylsulfoxide by (BDI)Nb(N(t)Bu)(CO)(2) led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(N(t)Bu)(NMes)(py) and [(BDI)Nb(N(t)Bu)](2)(μ2-O)(2), respectively. MeLi addition to (BDI)Nb(N(t)Bu)(CO)(2)(py) resulted in the formation of a Nb-acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb-C(acylate) bond distance (2.059(4) ?), consistent with multiple Nb-C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(N(t)Bu)(CO)(2) with two equivalents of 4,4'-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1: 1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. Relatedly, addition of 1-phenyl-1-propyne to (BDI)Nb(N(t)Bu)(CO)(2) formed a thermally unstable 1: 1 Nb/alkyne complex, as characterized by NMR and IR spectroscopies; reaction of this species with HCl/MeOH yielded a 2: 1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb-C bonds.     

富氮MeNx(Me=Ti,Zr,Hf)薄膜的结构与红外光学性能

用射频反应磁控溅射方法制备了MeNx(Me=Ti、Zr、Hf)薄膜,研究了在富N2条件下不同的N2/Ar流量比对薄膜结构和光学性能的影响.掠角X射线衍射的分析结果表明,所制得的富氮的TiNx薄膜主要由TiN所组成,而富氮的ZrNx、HfNx薄膜则具有非晶态的结构.用分光光度计和傅里叶红外仪对薄膜的光学透过率的测试表明,...     

Suppression of electrical breakdown in silicon nitride films deposited by catalytic chemical vapor deposition at temperatures below 200 degrees C

Silicon nitride (SiN(x)) films for a gate dielectric layer of thin film transistors were deposited by catalytic chemical vapor deposition at a low temperature (< or = 200 degrees C). A mixture of SiH4, NH3 and H2 was used as a source gas. Metal-insulator-semiconductor (MIS) capacitor structures were fabricated for current-voltage (I-V) and capacitance-voltage (C-V) measurements. The breakdown voltage characteristics of the SiN(x) films were improved by the increase of NH3/SiH4 and H2/SiH4 mixing ratios and substrate temperatures. H2 treatment was attempted to improve the breakdown voltage further. A breakdown voltage as high as 6.6 MV/cm was obtained after H2 annealing at 180 degrees C. The defect states inside the SiN(x) films were analyzed by photoluminescence spectra. Silicon dangling bonds (2.5 eV) and nitrogen dangling bonds (3.1 eV) were observed. These defect states inside the SiN(x) films disappeared after H2 annealing. Flat band voltage shifts were observed in C-V curves, and their magnitudes decreased as the defect states inside the SiN(x) films decreased.     

Studies on the Condensation Pathway to and Properties of Diiron Azadithiolate Carbonyls

Reaction of Fe(2)(SH)(2)(CO)(6) and HCHO, which gives Fe(2)[(SCH(2))(2)NH](CO)(6) in the presence of NH(3), affords the possible intermediate Fe(2)(SCH(2)OH)(2)(CO)(6), which has been characterized crystallographically as its axial-equatorial isomer. Fe(2)(SCH(2)OH)(2)(CO)(6) was shown to react with ammonia and amines to give Fe(2)[(SCH(2))(2)NR](CO)(6) (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe(2)(SH)(2)(CO)(6) with RC(O)C(O)R (R = H, Ph, 4-F-C(6)H(4)) to give cycloadducts. The benzil derivative Fe(2)[S(2)C(2)(OH)(2)Ph(2)](CO)(6), a C(2)-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe(2)[(SCH(2))(2)NAc](CO)(6) was prepared by reaction of Li(2)Fe(2)S(2)(CO)(6) with (ClCH(2))(2)NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe(2)[(SCH(2))(2)NAc](CO)(6) and Fe(2)[(SCH(2))(2)NAc](CO)(4)(PMe(3))(2), which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe(2)[(SCH(2))(2)NC(S)Me](CO)(6) does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.     

NiFe Nanoparticles: A Soft Magnetic Material?

Polytetrahedral NiFe nanoparticles with diameters of (2.8+/-0.3) nm have been obtained by hydrogenation of Ni[(COD)(2)] (COD=1,5-cyclooctadiene) and Fe[{N(SiMe(3))(2)}(2)] at 150 degrees C using stearic acid and hexadecylamine as stabilizing ligands. The nanoparticles are superparamagnetic at room temperature and display a blocking temperature of 17.6 K. Their anisotropy (2.7x10(5)J m(-3)) is determined to be more than two orders of magnitude higher than that of the bulk NiFe alloy (10(3)J m(-3)) and is close to that determined for Fe nanoparticles of the same size. Still, they display a magnetization of (1.69+/-0.05) mu(B) per metallic atom, identical to that of the bulk NiFe alloy. Combining the results from X-ray absorption and M?ssbauer studies, we evidence a progressive enrichment in iron atoms from the core to the surface of the nanoparticles. These results are discussed in relation to both size and chemical effects. They show the main role played by the enriched Fe surface on the magnetic properties and address the feasibility of soft magnetic materials at the nanoscale.     

Vibrational excitation in single-molecule transistors: deviation from the simple franck-condon prediction

We investigated the inner-sphere reorganization of ferrocene ((Cp) 2Fe ( n+ )) and tris(2,2'-bipyridine) iron ((bpy) 3Fe ( n+ )) in a single-molecule-transistor geometry. In (Cp) 2Fe ( n+ ) ( n = 0 and 1), almost no vibrations were excited during single-electron transport, whereas in (bpy) 3Fe ( n+ ) ( n = 1, 2, and 3), many distinct vibrations appeared, consistent with its larger reorganization energy. The observed excitation intensities varied significantly across devices, however, and could not be accounted for by "Franck-Condon" factors. This observation indicates that a quantitative account of electron-vibration coupling in single-electron tunneling requires further investigation.     

溶胶－凝胶法制备Pb（Zr，Ti）O_3玻璃陶瓷过程中的结构变化

本文介绍溶胶－凝胶法制备均匀ＰｂＺｒ－Ｔｉ－Ｂ－Ｓｉ凝胶玻璃，并通过适当热处理在凝胶玻璃中原位生长Ｐｂ（Ｚｒ；Ｔｉ）Ｏ３微晶的新工艺·利用ＩＲ谱考察了凝胶玻璃中的元素键合结构随温度的变化．结合热分析和ＸＲＤ；ＳＥＭ技术，研究了Ｐｂ（Ｚｒ，Ｔｉ）Ｏ３微晶在凝胶玻璃中的生长过程及该材料的结构特点．发现Ｐｂ２（Ｚｒ，Ｔｉ）２Ｏ６＋ｘ立方焦绿石介稳过渡相的纳米微晶首先出现于该体系中，并在更高的温度下先后完全转变成三方和四方Ｐｂ（Ｚｒ，Ｔｉ）Ｏ３钙钛矿相．电子显微观察结果表明，该工艺制备的Ｐｈ（Ｚｒ；Ｔｉ）Ｏ３玻璃陶瓷具有均匀的细晶结构．     

Mechanical properties of hot pressed SiCp and B4Cp/Alumix 123 composites alloyed with minor Zr

In the present study, effect of Zr addition on the microstructure and wear behavior of aluminum alloy composites (AMCs) reinforced with B4Cp and SiCp particles fabricated via hot pressing were investigated. The samples for the study composed of unreinforced aluminum alloy (Alumix 123) and the composites reinforced with 10% B4Cp and % SiCp were prepared by hot isostatic pressing (HIP) method. Similarly, all the samples alloyed with 0.2% Zr were also produced in order to make a comparison. The produced samples were evaluated for microstructural properties and mechanical tests for hardness, tensile and bending strength were performed. Wear test was carried out at 5 mm/s sliding speed under 3.0 N load for the all kind of hot pressed produced samples. The hot pressed composite microstructures have a more uniform distribution of the reinforcements. After HIP process, the composites were successfully produced with high density (>99%). The addition of Zr increased the yield and tensile strength of the samples. The highest strength value was found for the sample Al 123 matrix alloy with Zr. Evaluation of microstructures showed that copper and zirconium dispersed equally within the matrix microstructure without agglomeration. For the composite samples, Al3Zr, appeared as white precipitate, were inspected around B4C and SiC particles. The composite containing SiC particles and Zr had wear resistance value superior to those of the other counterparts.     

TiCp*(OMe)3 versus Ti(OMe)4 in atomic layer deposition of TiO2 with water--ab initio modelling of atomic layer deposition surface reactions

It is a common finding that titanocene-derived precursors do not yield TiO2 films in ALD with water. For instance, ALD with Ti(OMe)4 and water gives 0.5 A/cycle, while TiCp*(OMe)3 does not show any growth (Me=CH3, Cp* = C5(CH3)5). This is apparently in contradiction with the computed reactivity of the ligands: the energetics of hydrolysis of the gas-phase precursor indicate that TiCp*(OMe)3 is more reactive to ligand elimination than Ti(OMe)4. However such a model of precursor reactivity neglects surface reactions such as adsorption, diffusion and desorption, all of which can have an important effect on ALD growth rate. A more accurate model of the surface reaction is needed to find the reason for the different behaviours of Ti(OMe)4 and TiCp*(OMe)3 in the ALD process. The more realistic surface model is a TiO2 slab that is periodic in three dimensions. These calculations reveal that TiCp*(OMe)3 does not chemisorb in the usual way because of extreme crowding of the Ti centre by Cp* and that this prevents ALD growth.     

Influence of Nitrogen Flow Rate on the Microstructure and Properties of N and Me (Me=Cr,Zr) Co-doped Diamond-like Carbon Films

In this paper,Me (Me=Cr,Zr) and N co-doped diamond like carbon (DLC-MeN) composite films were prepared on cemented carbide substrates by pulsed bias arc ion plating.The effect of nitrogen flow rates on the microstructure and properties of the films were investigated by X-ray photoelectron spectroscopy (XPS),Raman spectra,grazing incident X-ray diffraction (GIXRD),high resolution transmission electron microscopy (HRTEM) and nano-indentation.Raman,GIXRD and HRTEM results show that the deposited films are nano...     

Piezoelectric ceramics with high dielectric constants for ultrasonic medical transducers

Complex system ceramics Pb(Sc(1/2)Nb(1/2))O3-Pb(Mg(1/3)Nb(2/3))O3-Pb(Ni(1/2)Nb(1/2))O3-(Pb0.965,Sr0.035) (Zr,Ti)O3 (PSN-PMN-PNN-PSZT abbreviated PSMNZT) have been synthesized by the conventional technique, and dielectric and piezoelectric properties of the ceramics have been investigated for ultrasonic medical transducers. High capacitances of the transducers are desired in order to match the electrical impedance between the transducers and the coaxial cable in array probes. Although piezoelectric ceramics that have high dielectric constants (epsilon33t/epsilon0 > 5000, k'33 < 70%) are produced in many foundries, the dielectric constants are insufficient. However, we have reported that low molecular mass B-site ions in the lead-perovskite structures are important in realizing better dielectric and piezoelectric properties. We focused on the complex system ceramics PSMNZT that consists of light B-site elements. The maximum dielectric constant, epsilon33T/epsilon0 = 7, 200, was confirmed in the ceramics, where k'33 = 69%, d33 = 940 pC/N, and T(c) = 135 degrees C were obtained. Moreover, pulse-echo characteristics were simulated using the Mason model. The PSMNZT ceramic probe showed echo amplitude about 5.5 dB higher than that of the conventional PZT ceramic probe (PZT-5H type). In this paper, the electrical properties of the PSMNZT ceramics and the simulation results for pulse-echo characteristics of the phased-array probes are introduced.     

High-basicity determination in mixed water-alcohol solutions by a dual optical sensor approach

The activity of NaOH is known to be significantly affected by the presence of an alcohol in aqueous solutions. A novel linear relationship between (deltaA/deltaC(alcohol)) and C(base) was found in the highly alkaline, mixed H2O-ROH solutions (R = Me, Et, i-Pr). The use of this linear relationship led to a dual-transducer approach to decompose the optical signals of optical base sensors and to give base and alcohol concentrations in concentrated NaOH-H2O-ROH solutions ([OH-] = 0.05-3.6 M). The scope of the new dual-sensor approach was evaluated, and errors in C(base) and C(alcohol) were analyzed. The optical base sensors consist of sol-gel SiO2-ZrO2-organic polymer composites doped with high-pKa indicators. The pKa(s) of the indicators encapsulated in the composite films were determined and found to be affected by the composition of the sol-gel composites. Optical sensors and their uses in multicomponent systems are of intense current interest.( 1-7) In the multicomponent systems, the activity of the analyte and sensor response are often affected by change in ionic strength. For optical sensors that are based on indicator equilibria involving the analyte as their transducing mechanism, such effect is particularly significant. The concentrations of both the analyte and other chemicals affect ionic strength, and the sensor response to concentration of the analyte is thus often indistinguishable from those of other chemicals. An accurate measurement of each component in these multicomponent systems is actively studied. Several approaches have been developed to correct ionic strength in optical sensing for the pH region and solutions of low-to-medium ionic strength. (1-9) We recently reported a dual-transducer approach to measure acid concentrations (2-9 M HCl) in salt-containing, concentrated strong acids such as MClx-HCl (M = Li, Ca, Al) solutions. (10) This approach was shown to reduce the error in C(acid) from, for example,     

Scope and Mechanistic Study of the Coupling Reaction of α, β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C-H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1](1)[propene](0)[cinnamate](-1). A negligible deuterium kinetic isotope effect (k(H)/k(D) = 1.1±0.1) was measured from both (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) and (E)-C(6)H(5)CD=C(CH(3))CONHCH(3) with styrene. In contrast, a significant normal isotope effect (k(H)/k(D) = 1.7±0.1) was observed from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene and styrene-d(10). A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C(6)H(5)CH=CHCO(2)Et with propene ((13)C(recovered)/(13)C(virgin) at C(β) = 1.019(6)), while a negligible carbon isotope effect ((13)C(recovered)/(13)C(virgin) at C(β) = 0.999(4)) was obtained from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene. Hammett plots from the correlation of para-substituted p-X-C(6)H(4)CH=CHCO(2)Et (X = OCH(3), CH(3), H, F, Cl, CO(2)Me, CF(3)) with propene and from the treatment of (E)-C(6)H(5)CH=CHCO(2)Et with a series of para-substituted styrenes p-Y-C(6)H(4)CH=CH(2) (Y = OCH(3), CH(3), H, F, Cl, CF(3)) gave the positive slopes for both cases (ρ = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, Δ H(?) = 20±2 kcal mol(-1) and S(?) = -42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies.     

Synthesis of ditungsten carbide by controlled decomposition of Cp2W2(CO)4 (dmad) under a hydrogen atmosphere

Controlled decomposition studies of the bis(cyclopentadienyl)ditungsten(tetracarbonyl)-dimethylacetylenedicarboxylate (Cp2W2(CO)4(dmad)) under flowing hydrogen show that it totally decomposes at 600 °C for 2 h to give a pure bulk W2C as revealed by X-ray diffraction. Excess oxygen and carbon at the surface are detected by X-ray photoelectron spectroscopy. An in situ temperature-programmed X-ray diffraction experiment performed on Cp2W2(CO)4 (dmad) shows the detection temperature of W2C to be 600 °C, the sample being amorphous or microcrystalline below that temperature. Based on previous results obtained for the decomposition of Cp2Mo2(CO)4(dmad) on the one hand, and thermogravimetric and chromatographic analyses performed on Cp2W2(CO)4 (dmad), on the other, a decomposition scheme of the latter under hydrogen has been proposed. © 1998 Chapman & Hall