C-H Activation and C-C coupling of arenes by cationic Pt(II) complexes

The synthesis and characterization of cationic platinum complexes of the type [(R(2)PC(2)H(4)PR(2))PtMe(OEt(2))]BAr(F) (R = Cy, Et) are reported. These electrophilic platinum cations are found to react quantitatively with arenes (benzene, toluene) at room temperature by undergoing intermolecular C-H activation with concomitant C-C coupling to generate complexes of the type [[Pt(R(2)PC(2)H(4)PR(2))](2)(mu-eta(3):eta(3)-biaryl)][BAr(F)](2). The dianionic biaryl ligands in these compounds exhibit a rare mu-eta(3):eta(3)-bis-allyl bonding mode and can be removed from the complex with stoichiometric oxidants to generate the free biaryl and [(R(2)PC(2)H(4)PR(2))Pt(mu-X)](2)[BAr(F)](2) (R = Cy, Et; X = Cl, I). The cationic platinum complexes [(R(2)PC(2)H(4)PR(2))PtMe(OEt(2))]BAr(F) (R = Cy, Et) are also quite reactive with water, forming the bridging hydroxide complexes [(R(2)PC(2)H(4)PR(2))Pt(mu-OH)](2)[BAr(F)](2) (R = Cy, Et). A possible mechanism is proposed for the C-C coupling reaction based upon the structures of these bridging biphenyl complexes, which provides a new perspective for the related palladium-catalyzed oxidative coupling of arenes to form biaryls.     

非参数自回归模型异方差的小波检验

本文讨论了非参数自回归模型异方差的检验问题.在非参数自回归模型的建模过程中,通常假定方差为常数.然而在建模前,我们应该首先检验这-假定是否成立.本文将利用小波方法来检验异方差问题.我们首先利用核估计方法定义经验小波系数,然后讨论其渐近性质.在此基础上,我们提出了异方差性检验的统计量.数值模拟结果表明,我们的方法表现良好.     

Synthesis and Characterization of a Series of Triethylphosphine-Ligated Pt-Au Cluster Compounds. X-ray Crystal and Molecular Structure of [Pt(AuPEt(3))(9)](NO(3))(3)

The first triethylphosphine-stabilized Pt-Au cluster compounds, [Pt(AuPEt(3))(10)](2+) (2) and [Pt(AuPEt(3))(9)](3+) (3), were prepared by the direct reaction of Pt(PEt(3))(3) with AuPEt(3)NO(3) under a dihydrogen atmosphere. Cluster 2 is the highest-nuclearity homoleptic Pt(AuPR(3))(n)() cluster yet prepared. The reactivity and structures of these clusters are in agreement with the well-established electron-counting arguments. The 18-electron cluster 2 was converted into the 16-electron cluster 3 by oxidation with 2 equiv of ferricinium ion [Fe(eta(5)-C(5)H(5))(2)](+). Cluster 3 was converted into 2 by reduction with H(2) in the presence of [AuPEt(3)](+). Cluster 3 was also observed to cleanly add the 2-electron donors CO and PEt(3) to form the 18-electron clusters [(CO)Pt(AuPEt(3))(9)](3+) (4) and [(PEt(3))Pt(AuPEt(3))(9)](3+) (5), respectively. Single-crystal X-ray diffraction results show that 3 has a flattened, toroidal structure in which the PtAu(9) framework has a Pt-centered, tricapped trigonal prismatic geometry. Crystal data for [Pt(AuPEt(3))(9)](NO(3))(3) is as follows: hexagonal P6(3)/m, a = 15.134(5) ?, c = 23.48(1) ?, V = 4657 ?(3), Z = 2, residuals R = 0.056, and R(w)() = 0.053 for 1489 observed reflections and 81 variables, Mo Kalpha radiation. Compound 3 was found to reversibly add H(2) in solution to form the dihydride cluster [(H)(2)Pt(AuPEt(3))(9)](3+) (6). The equilibrium constant for this addition reaction is 1.1 x 10(3) M(-)(1) (CD(2)Cl(2) solution, 25 degrees C), slightly smaller than that for [Pt(AuPPh(3))(8)](2+). The rate of the addition is also slower than that with [Pt(AuPPh(3))(8)](2+). Cluster 3 is an excellent homogeneous catalyst for H(2)-D(2) equilibration giving a turnover rate for HD production of 0.13 s(-)(1) (nitrobenzene solvent, 30 degrees C, 1 atm). The PEt(3)-containing clusters give similar rates and follow the same general trends previously observed with PPh(3)-ligated clusters. The chemistry of these new clusters is explained by consideration of the steric and electronic properties of the PEt(3) ligand. These new compounds will be useful as models for hydrogen activation by Pt-Au clusters and as precursors for supported Pt-Au catalysts.     

集值序上鞅的若干有关问题

本文研究了连续时间的集值序上鞅,在一定的假设下我们证明了集值序上鞅有ｈ－Ｒｉｅｓｚ分解,然后证明了集值序上鞅的Ｄｏｏｂ－Ｍｅｙｅｒ分解定理。     

Characteristics of the sampling paddle modules of neutron wall from the cosmic ray test

In the construction of a large area neutron detector(neutron wall)that is used to detect neutrons at GeV energies,the performances of all the sampling paddle modules prepared for the neutron wall areinvestigated with a specially designed test bench.Tested by cosmic rays,an average intrinsic time resolution of 222.5 ps is achieved at the center of the modules.The light attenuation length and the effective speed of the light in the module are also investigated.     

Study of BESⅢ MUC offline software with cosmic-ray data

Cosmic-ray data of 90 M events have been collected and used for calibration, alignment as well as detector tuning. A special tracking algorithm for the BESⅢ muon counter is developed and verified with Monte-Carlo simulation and then further confirmed with the cosmic-ray data. The obtained strip resolutions are in good agreement with the design values. A new alignment approach for the BESⅢ muon counter is confirmed with the cosmic-ray data and proposed to be used in future analysis of experimental data.     

Direct Observation of NN Pairs Transfer in GaP1-xNx （x=0.12%）

Time-resolved photoluminescence （TRPL） was applied to investigate the transient process in GaP1-xNx （x = 0.12%） alloy. The filling, transferring and decay processes among nitrogen pairs are directly observed. The NN4 pair, either not present or only a small obscure peak under a proper excitation condition in the steady-state photoluminescence spectrum, is well resolved by TRPL.     

数值序上鞅的若干有关问题

本文研究了连续时间的集值序上鞅．在一定的假设下我们证明了集值序上鞅有ｈ－Ｒｉｅｓｚ分解,然后证明了集值序上鞅的Ｄｏｏｂ－Ｍｅｙｅｒ分解定理．