Cesium dimethyltetrachloroplatinate,a complex of dimethylplatinum(IV). Synthesis and some reductive elimination reactions involving the monomethylplatinum(II) complex as an intermediate

The reduction of Pt(IV) complexes followed by the oxidative addition of dimethyl sulfate to Pt(II) affords Cs₂PtMe₂Cl₄, a complex of dimethylplatinum(IV). On treatment with such nucleophiles as Cl^–, Br^–, I^–, and PtCl₄ ^2– in aqueous solutions at 368 K this complex undergoes reductive elimination to give MeX and Pt^IIMe as a transient species. The latter is further converted to methane upon protolysis, whereas in the presence of an oxidant (Na₂PtCl₆) it gives rise to the Pt^IVMe species. The kinetics of decomposition of Cs₂PtMe₂Cl₄ in aqueous HCl-KCl systems (2M or 3M in Cl^–; [Pt^IVMe₂][Cl^–]) were studied. The reaction takes place as anS _N 2 attack of X^– on the carbon atom of a methyl group located with thetrans position with respect to the aqua-ligand of the [PtMe₂Cl₃(H₂O)]^– complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 389–395, February, 1993.     

Reaction of trans-[Pt(H)2(PCy3)2] with C60 reductive elimination of H2 and formation of [Pt(PCy3)2(η-C60)]

Reaction of trans-[Pt(H)₂(PCy₃)₂], 1, with [60]fullerene at room temperature affords [Pt(PCy₃)₂(η²-C₆₀)], 2, in nearly quantitative yield. The most probable reaction pattern is the insertion of a fullerene 6,6 junction onto a Pt-H bond yielding an η¹ alkyl derivative which, after hydrogen extrusion, gives 2. On the other hand, addition of 1 to different electron-deficient olefins, such as dimethyl maleate and fumarate, furnishes mixtures of both η¹ metal—alkyl and η² metal—olefin derivatives. If tetrachloroethylene is used as 2π component, trans-[PtCl(H)(PCy₃)₂] forms exclusively.     

酞菁类化合物对MH/Ni电池性能的影响

针对MH/Ni电池充电过程中氧的产生和不恰当的消除方式带来的内压升高和热量聚集使电池总体性能衰减很快的问题, 提出采用降低化学催化氧还原的比例, 提高热量产生少的电催化氧还原比例的方法加以解决.金属酞菁类化合物是一种电催化氧还原剂.添加酞菁的MH/Ni电池与对比电池进行容量衰减、内压、大电流放电等特性比较, 其性能均有显著提高.     

Ab initio and density functional theory studies on the mechanism of nucleophilic vinylic substitution of 4<Emphasis Type="Italic">H</Emphasis>-pyran-4-one and 2-methyl-4<Emphasis Type="Italic">H</Emphasis>-pyran-4-one with ammonia

 Nucleophilic vinylic substitutions of 4H-pyran-4-one and 2-methyl-4H-pyran-4-one with ammonia were calculated by the B3LYP method using the 6-31G(d,p) basis set. Bulk solvent effects of aqueous solution were estimated by the polarized continuum and Poisson–Boltzmann self-consistent reaction field models using the 6-311+G(d,p) basis set. In the gas phase different mechanisms were found for the two reaction systems calculated. The reaction of 4H-pyran-4-one proceeds through enol, whereas a feasible path for the less reactive 2-methyl-4H-pyran-4-one is the mechanism through a keto intermediate. Addition of ammonia in concert with proton transfer is the rate-determining step ofthe reaction. The mechanism proceeding either by a bimolecular nucleophilic substitution (S_N2) or by one involving a tetrahedral zwitterionic intermediate is shown to be unlikely in the gas phase or nonpolar solution. The effects of bulk solvent not only consist in a reduction of the various activation barriers by about 25–40 kJ mol⁻¹ but also in a change in the reaction mechanism. Received 26 May 2002 / Accepted 26 July 2002 / Published online: 14 February 2003     

基于自适应逆控制技术的船舶操纵仿真控制

对自适应逆控制理论中的对象动态控制问题和对象扰动控制问题分别进行了探讨，并且针对船舶模型特性，改进了自适应逆控制的框图，使其能够更好地应用于船舶操纵控制。在算法上用最小二乘法代替LMS(Least Mean Square)算法对船舶进行模型参数辨识和控制器的设计。仿真结果表明，改进后的自适应逆控制算法能适应船舶数学模型的变化，与PID控制相比，这种算法具有动态响应快，抗扰动性好等特点。     

冻融条件下软岩隧道冻胀力计算分析

针对软岩体含水率高、孔隙率大、对温度变化敏感等特点,本文首先在一定假设的基础上,分析了温度影响范围内软岩体冻结后,内部水冰相变会导致隧道衬砌承受冻胀力的原因,推导出了其弹性力学解,其次分析了融化过程及融化后冻胀力变化的过程及原因,运用弹性力学复变函数法推导出了冻融后隧道衬砌所承受冻胀力的表达式,最后给出了算例并指出将来的研究方向。     

数字图像中照度不均匀校正技术研究

为了消除数字图像中的照度不均匀性，对现有数字图像的照度不均匀校正技术进行了归类和讨论．分析了这些方法在计算误差上的内在原因，并在此基础上提出了基于小波变换的数字图像照度不均匀校正技术．该技术兼顾了数字图像的频域和空域，使得采用本方法校正后的图像具有品质优，计算误差小和时间消耗较少等特点．     

180 000kVA及以下容量变压器全自冷方式设计探讨

针对常规180 000kVA及以下容量变压器采用的传统冷却方式,提出并实施了一种从用户运行维护及节能角度出发的新的冷却模式,即全自冷方式冷却,并结合实例进行了分析.     

中高压变频装置的状态自适应运行监控系统

为保证6kV/1600kVA变频调速装置的可靠运行,设计了状态自适应的一体化运行监测与控制系统(OMCS),为保证系统的可靠、实时性,硬件系统采用P 700MHz/128MB内存的工控机和A/D转速速率高达800MHz/通道的AI卡,软件系统是基于该文所提出的状态自适应监控逻辑。OMCS的平均监测周期为20ms。试验期间所发生的2次AI卡故障、2次脉冲发生器异常、各保护动作情况及脉冲封锁后并联滤波电容与异步电机的自激等均被OMCS监测到。这些结果表明OMCS对提高变频装置的性能具有重要作用。     

工业铝厂富水氢氧化铝污泥冻结点的测定

依据冻结点测定原理和污泥内水分存在的多种形式 ,测定了工业铝厂富水氢氧化铝污泥冷冻过程中温度和电阻随时间变化的工作曲线 ,得到该污泥冻结点为 - 1.3～ - 3.0℃ ,与冷冻环境温度无关 .