Synthesis and reactivity of η-tetramethylcyclopentadienyl-propenyl rhenium complexes: Molecular structure of [(η:η-C5Me4CH2CHCH2)Re(CO)2]

The fulvene complexes [(η⁶-C₅Me₄CH₂)Re(CO)₂(R)] (1a, RI; 1b, RC₆F₅) react at the exocyclic methylene carbon with a vinylmagnesium bromide solution to produce the anionic species [(η⁵-C₅Me₄CH₂CHCH₂)Re(CO)₂(R)]⁻. Protonation with HCl at 0 °C produces the hydride complexes [trans-(η⁵-C₅Me₄CH₂CHCH₂)Re(CO)₂(R)(H)] (2a, RI; 2b, RC₆F₅). Thermolysis of an hexane solution of the iodo-hydride (2a) under a CO atmosphere yields the complex [(η⁵-C₅Me₄CH₂CHCH₂)Re(CO)₃] (3) and [Re(CO)₅I] as by-product. Thermolysis of 2b produced three new products, mainly the chelated complex [(η⁵:η²-C₅Me₄CH₂CHCH₂)Re(CO)₂] (4) and complex 3, with a non-coordinated olefin group, in moderated yield, and traces of [Re(CO)₅(C₆F₅)]. Thermolysis of an hexane solution of 2 in presence of an excess of PMe₃, afforded the phosphine derivative [(η⁵-C₅Me₄CH₂CHCH₂)Re(CO)₂(PMe₃)] (5). All the complexes were characterized by IR, ¹H, ¹³C and ³¹P NMR spectroscopies and mass spectrometry. The molecular structure of 4 has also been determined. The molecule exhibits a formal three-legged piano-stool structure, with two CO groups, and the third position corresponding to the η²-coordination of the propenyl side arm of the η⁵-C₅Me₄ ring.     

Orbit determination and time synchronization for a GEO/IGSO satellite navigation constellation with regional tracking network

Aiming at regional services,the space segment of COMPASS (Phase I) satellite navigation system is a constellation of Geostationary Earth Orbit (GEO),Inclined Geostationary Earth Orbit (IGSO) and Medium Earth Orbit (MEO) satellites.Precise orbit determination (POD) for the satellites is limited by the geographic distribution of regional tracking stations.Independent time synchronization (TS) system is developed to supplement the regional tracking network,and satellite clock errors and orbit data may be obtai...     

射流影响下气固两相流动试验的定量分析

为了研究受限空间内的射流影响下的气固两相流动,本文采用数码颗粒图像测速仪（DpIV）系统测量颗粒分布,并开发了一套用于处理DPIV颗粒图片的算法,可用于准确地定量分析通道内的颗粒分布。使用该算法能够获得颗粒在拍摄平面内的二维相对浓度数据,定量分析该数据发现,在同样的流场条件下,射流对气流场和不同粒径颗粒的影响区域存在明...     

Requiem for the Miller–Tucker–Zemlin subtour elimination constraints?

The Miller–Tucker–Zemlin (MTZ) Subtour Elimination Constraints (SECs) and the improved version by Desrochers and Laporte (DL) have been and are still in regular use to model a variety of routing problems. This paper presents a systematic way of deriving inequalities that are more complicated than the MTZ and DL inequalities and that, in a certain way, “generalize” the underlying idea of the original inequalities. We present a polyhedral approach that studies and analyses the convex hull of feasible sets for small dimensions. This approach allows us to generate generalizations of the MTZ and DL inequalities, which are “good” in the sense that they define facets of these small polyhedra. It is well known that DL inequalities imply a subset of Dantzig–Fulkerson–Johnson (DFJ) SECs for two-node subsets. Through the approach presented, we describe a generalization of these inequalities which imply DFJ SECs for three-node subsets and show that generalizations for larger subsets are unlikely to exist. Our study presents a similar analysis with generalizations of MTZ inequalities and their relation with the lifted circuit inequalities for three node subsets.     

Schiff bases derived from p-aminobenzyl alcohol as trigger groups for pH-dependent prodrug activation

A number of novel acid-sensitive Schiff bases derived from p-aminobenzyl alcohol and various benzaldehyde derivatives were synthesized and were subsequently shown to trigger benzyl elimination reactions. The kinetics of acid-catalyzed hydrolysis at pH 5.0 as well as stability at pH 7.4 were studied using fluorogenic model compounds. Two fluoro-substituted Schiff bases showed efficient hydrolysis at pH 5.0 combined with a long-term stability at pH 7.4 and are considered suitable candidates for the development of anticancer prodrugs.     

Theoretical study on electronic structure of (CNC)Fe_2N2 and its N2 elimination mechanism

The density function theory (DFT) is to elucidate the electronic structure of bis(dinitrogen) Fe(0) complex, (CNC)Fe_2N₂, and its N₂ elimination mechanism. (CNC)Fe_2N₂ has a low‐spin singlet (S = 0) ground state with a distorted square pyramidal structure. Fragment orbital interaction analysis yields total occupancy of π* orbitals (LUF₍₄₎O and LUF₍₄₎O−1) of apical N3 N4 is 0.188 while that of basal N1 N2 is 0.187 in ^S0(CNC)Fe_2N₂, suggesting nearly the same activation extent for both basal and apical N₂ ligands. The lowest‐lying triplet state T₁ (3‐A′) has a repulsive potential energy surface along the Fe N3 bong length by PBE functional, while a minimum on T₂ state (3‐A″) with higher energy is found by B3LYP functional. The nonadiabatic N₂ elimination mechanism of (CNC)Fe_2N₂ involves an S₀‐T₁ states crossing, which lowers the activation energy to 9.7 kcal/mol and produces high‐spin intermediate (CNC)Fe N₂. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Rounding Error Analysis in Solving M-Matrix Linear Systems of Block Hessenberg Form

The problem of solving large M-matrix linear systems with sparse coefficient matrix in block Hessenberg form is here addressed. In previous work of the authors a divide-and-conquer strategy was proposed and a backward error analysis of the resulting algorithm was presented showing its effectiveness for the solution of computational problems of queueing theory and Markov chains. In particular, it was shown that for block Hessenberg M-matrices the algorithm is weakly backward stable in the sense that the computed solution is the exact solution of a nearby linear system, where the norm of the perturbation is proportional to the condition number of the coefficient matrix. In this note a better error estimate is given by showing that for block Hessenberg M-matrices the algorithm is even backward stable.     

基于多项式组主项解耦消元法的几何定理机器证明

基于多项式组主项解耦消元法 ,将几何定理的假设条件 (多项式组 PS)化为主项只含主变元的三角型多项式组 DTS,可得到定理命题成立的不含变元的非退化条件 ,即充分必要或更接近充分必要的非退化条件 .由于多项式主系数不含变元 ,已不存在 DTS多项式之间的约化问题 ,故方法有普遍意义 .文中例为西姆松定理的机器证明 .     

Synthetic approach to pentacyclic quassinoids from communic acids, via ambracetal derivatives

Methyl (8R,13S)-8α,13:13,17-diepoxy-14,15-dinorlabdane-19-oate, easily prepared from communic acids, is a suitable intermediate for synthesizing pentacyclic quassinoids, because it enables the elaboration of the A ring and the further construction of the B-C-D ring system of these terpenoids. The cetal group is stable under the reaction conditions utilized during the elimination of the ester group and the introduction of the hydroxyl group on C-3. At the same time, it enables the regeneration of the methylketone and exocyclic double bond presented by methyl 13-oxo-14,15-dinorlabd-8(17)en-19-oate. The latter compound was previously used to construct the B-C-D-ring of these quassinoids.