Reaction of ruthenium carbonylcarbide cluster Ru6C(CO)17 with nickelocene and pentamethylcyclopentadiene

The reaction of cluster Ru₆C(CO)₁₇ (1) with nickelocene is studied. Five CO ligands rather than a metal-ligand crown are substituted for two cyclopentadienyl groups to give a new complex Ru₆C(⁵-Cp)₂(CO)₁₂ (2). The reaction of cluster1 with entamethylcyclopentadiene leads to new complex Ru₆C(-¹⁵-CH₂C₅Me₄)(CO)₁₄ (3) containing the cr-bond CH₂-Ru, along with an ⁵-coordinated cyclopentadienyl ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1171–1172, June, 1995.     

First principles study of small palladium cluster growth and isomerization

Structures and physical properties of small palladium clusters Pd_n up to n = 15 and several selected larger clusters were studied using density functional theory under the generalized gradient approximation. It was found that small Pd_n clusters begin to grow 3‐dimensionally at n = 4 and evolve into symmetric geometric configurations, such as icosahedral and fcc‐like, near n = 15. Several isomers with nearly degenerate average binding energies were found to coexist and the physical properties of these clusters were calculated. For several selected isomers, relatively moderate energy barriers for structural interchange for a given cluster size were found, implying that isomerization could readily occur under ambient conditions. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Preparation and reactivity of metal-containing monomers

Mono- and disubstituted cluster metal-containing monomers were obtained under mild conditions on interaction of Rh₆(CO)₁₆ with 4-vinylpyridine (4-ViPy) in the presence of N-trimethylaminoxide. These products were characterized by IR and¹H NMR spectroscopy and by elemental and X-ray analyses. Rh₆(CO)₁₅(4-ViPy) was found to be an octahedral cluster with eleven terminal and four ₃-bridging carbonyl ligands. 4-ViPy is linked with the Rh(3) atom through the N atom and occupies the coordination site of the twelfth CO terminal ligand. The mean value of the Rh-Rh bond length is 2.762 Å. The unsaturated ligand has little or no effect on the geometry of the starting cluster and its double bond retains the ability to undergo addition reactions.For part 28, seeRuss. Chem. Bull., 1993, 453.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 975–979, May, 1993.     

铜对钌改性尖晶石催化剂结构和氧化性能的影响

通过湿化学法制备钌改性的纳米尖晶石MnFe1.95Ru0.05O4催化剂, 考察了添加助剂铜对该催化剂的影响.通过比表面积和孔径分布表征结果证实, 铜助剂的添加有效地增大了比表面积和孔容.XPS的测试结果表明, 钌的改性大大改变了尖晶石中各元素如锰和铁的化学环境；助剂铜的添加对于锰和铁等原子的影响不大, 但对钌原子的影响显著；EXAFS表征结果显示了铜助剂的导入影响了钌的周围环境, 形成了活性Ru=O键.以桂皮醇和苯甲醇的氧化反应为典型反应考察了添加助剂铜前后的影响.     

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)₂bpy]²⁺) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)₂bpy]²⁺ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)₂bpy]²⁺. The UV‐vis spectrophotometric results indicate that the [Ru(phend)₂bpy]²⁺ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)₂bpy]²⁺ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.     

CnBδ(δ=0, ±1; n =1～6)团簇的结构、稳定性和光谱

采用密度泛函理论(DFT)的B3LYP方法,在6-31G*和6-311＋G(3df)水平上对C_nB(n=1～6)团簇及其阴离子和阳离子的几何构型和电子结构进行了优化和振动频率计算.得到了C_nB(n=1～6)团簇的电离能,绝热电子亲合势以及C_nB^δ(δ=0,±1)团簇的能隙.结果表明C_nB^－(n=1～6)团簇的基态构型均为线形,这与等电子的C_n簇合物的结构是一致的; C_nB(n=1～6)团簇的基态构型中,除C₂B为不对称的三角形,C₆B为具有C_2v对称性的环状结构外,其余均为线形结构.阳离子团簇中n=2、3、6的基态结构具有C_2v对称性外,其它几个均为线形结构.从几何参数和振动频率上发现,采用密度泛函B3LYP方法在6-311＋G(3df)和6-31G*两种基组上计算得到的键长参数和振动频率非常接近,说明B3LYP方法在计算C_nB簇合物结构参数上对于基组的选择是不太敏感的.通过对C_nB(n=1～6)的光电子能谱性质的研究发现,C₄B容易获得一个电子形成阴离子团簇,但失去一个电子是很困难的,这与实验上观测到的结果非常吻合.     

Nonequilibrium dynamics of a diffusion-limited reaction driven by a cluster-memory mechanism

The diffusion-limited reaction A+AA+B is studied in general dimension. The asymptotic decay of the system is found to depend nontrivially upon the initial concentration of A particles for certain ranges of the diffusion constant, backward reaction rate, and total concentration of particles. This nonequilibrium behavior is due to the formation of clusters centered about the initial A particles. A perturbative analysis ind=1 shows that the transition to the nonequilibrium dynamics is sharp and is quite similar to another previously studied reaction A+AA. Ford>1, a scaling argument is presented which describes the dependence of the asymptotic decay on the initial concentration of A particles and the equilibrium concentration for large backward reaction rates. Monte Carlo data are shown which confirm the analytic work ind=1, 2, and 3.     

Evolution of the structural stability of large Cu,Ni, Pd,and Ag clusters with size: An analysis within the embedded atom method

A study of the structural stability of clusters made up of a single component has been carried out within the Embedded Atom Method. Perfect icosahedral and cuboctahedral Cu, Ni, Pd, and Ag clusters with up to 5083 atoms have been compared. The icosahedron is found to be the stable structure for small clusters, and a change of structure from icosahedral to cuboctahedral is found as the cluster size increases. A contraction of the interatomic distances results when the cluster size decreases.     

Defect clusters and precipitation/oxidation of MgO-Co1−xO solid solution

MgO and Co_1−xO powders in 9:1 and 1:9 molar ratio (denoted as M₉C₁ and M₁C₉, respectively) were sintered and homogenized at 1600°C followed by annealing at 850°C and 800°C, respectively to form defect clusters and precipitates. Analytical electron microscopic observations indicated the protoxide remained as rock salt structure with complicated planar diffraction contrast for M₉C₁ sample, however with spinel paracrystal precipitated from the M₁C₉ sample due to the assembly of charge- and volume-compensating defects of the 4:1 type, i.e., four octahedral vacant sites surrounding one Co³⁺-filled tetrahedral interstitial site. The spacing of such defect clusters is 4.5 times the lattice spacing of the average spinel structure of Mg-doped Co_3−δO₄, indicating a higher defect cluster concentration than undoped Co_3−δO₄. The {111} faulting of Mg-doped Co_3−δO₄/Co_1−xO in the annealed M₁C₉ sample implies the possible presence of zinc blend-type defect clusters with cation vacancies assembled along oxygen close packed (111) plane.     

Novel structure-defined chiral bis(oxazolinyl)thiophenes for Ru-catalyzed asymmetric cyclopropanation

The novel structures of sulfur-containing chiral bis(oxazoline) compounds which have been synthesized have been determined by X-ray crystal diffraction analyses. A high enantioselectivity (ee >99%) in the asymmetric cyclopropanation of diphenylethene with diazoester using the bis(oxazoline)-Ru(II) catalyst was obtained.