Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.     

Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.     

Pt羰基簇合物在NaY内的合成机理

利用IR，EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n＝3,4)在NaY分子筛超笼内的合成机理．在氧化样品Pt~(2+)/NaY上300－373 K的还愿羰基化过程中，首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)＝2110 cm~(-1))，然后聚集成“Pt_3(CO)_6”(σ_(CO)＝2112，1896和1841 cm~(-1))，最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)＝2080，1824 cm~(-1))．“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换，而[Pt_3(CO)_6]~(2-)_n(n＝3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢，室温下，NO能逐步破坏Pt羰基簇合物的层间和层内Pt－Pt键，得到中间物种“Pt_3(CO)_6”和PtO(CO)，同时在气相产生CO_2和N_2O．而由上述两中间物种出发，300－353 K温度下，在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物．     

一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构

The reactions of 18-crown-6 with Na₂[M(SCN)₄] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}₂(H₂O)]_n[Pd(SCN)₄]_n and complex 2 [{Na(18-C-6)}₂(H₂O)]_n[Pt(SCN)₄]_n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P2₁/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm³,Z=2,D_calcd=1.460g·cm^-3,F(000)=964,R₁=0.0406,wR₂=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm³,Z=2,D_calcd=1.690g·cm^-3,F(000)=1028,R₁=0.0292,wR₂=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}₂(H₂O)]²⁺ complex cations and [M(SCN)₄]^2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions.     

Kinetics of underpotential deposition and nucleation of copper on the Pt(111) face in the presence of acetonitrile

The kinetics of underpotential deposition, three-dimensional nucleation, and growth of copper deposits at cathodic overpotentials on a Pt(111) electrode in solutions containing 0.5 M H₂SO₄, 10 mM CuSO₄, and 0–200 mM acetonitrile (AcN) is studied by the cyclic voltammetry, potentiostatic current transients, and scanning probe microscopy methods. At low volume concentrations of acetonitrile ([AcN] ≤ 4 mM), adsorbed acetonitrile molecules accelerate the formation of a co-adsorption lattice of copper adatoms with anions due to local electrostatic effects at the charged interface. At higher concentrations, the underpotential deposition process is hampered, but the desorption of copper adatoms occurs at potentials more positive than those at low acetonitrile concentrations. This effect is attributed to a stabilizing action of acetonitrile molecules situated on the layer of copper adatoms and, in part, on platinum. At [AcN] = 0.4–40 mM, adsorbed acetonitrile molecules accelerate the growth of the bulk copper deposit, but the nucleation stage is hindered. The dependence of the copper amount on the deposition potential at [AcN] = 40 mM exhibits a maximum at 0.15–0.17 V. This effect was previously observed in weakly acid solutions (pH 1.7–3.0) containing no acetonitrile. The maximum rate of the deposit growth corresponds to an optimum number of crystallites (which is not too great) and an optimum distance between the growing centers in conditions of mixed kinetics “diffusion + electron transfer.” A substantial number of complexes Cu(I)-AcN forms at high acetonitrile concentrations.     

无机胶体法制备Pt/C催化剂及其性能表征

采用无机胶体法制备用于质子交换膜燃料电池(PEMFC)的Pt/C催化剂。研究了影响PtO₂胶体生成和稳定性的因素(溶液的pH值、浓度和温度条件等)以及不同还原剂浓度对Pt/C催化剂性能的影响。透射电子显微镜测试结果表明，采用经优化的工艺条件所制备的Pt/C催化剂平均粒径为3 nm，且分散性好、粒度均匀。X-射线衍射分析表明，催化剂中Pt(111)晶面的相对含量较高，有利于加速氧还原反应。单体PEMFC的电压/电流密度曲线测试表明，所制备的Pt/C催化剂具有良好的电化学性能。     

Two-dimensional catena–polymer [[[bis (µ-aqua)(bis (µ-cpiap-K2O1:O2)sodium(I))] (µ-chlorido) bis(µ-cpiap-K5N1:O1:O2:O3,O3′)dicopper(II)]bis(µ-aqua)(aqua)bis(cpiap-K2O1,O2)copper(II)] hexa hydrate

The new title two-dimensional hetero-tetra nuclear Cu₃–Na coordination polymer {[NaCu₃Cl(cpiap)₂(H₂O)₃]_n·6nH₂O} (1) consists of crystallographically two-independent copper(II) centers, each bridged by a sodium cation through carboxylate-oxygen of the deprotonated H₃cpiap ligand (H₃cpiap = 2-(carboxyphenyl)iminoaceticpropanoic acid) to Cu^II (2) and Cu^II (2⁻) cations, and through water molecules to Cu^II (1) cation. Cu^II (2) and Cu^II (1) cations are bridged by carboxylate-oxygen atoms of the ligand in a syn-anti mode which, alternate regularly within the chain being bridged by a tetra coordinated sodium cation. Each Cu^II (2) and Cu^II (2⁻) cation in (1) is in an octahedral environment formed by four carboxylate-oxygens from two cpiap³⁻ ligands, one nitrogen atom and a bridging chloride atom. Cu^II (1) cation is in a square pyramidal environment formed by three water molecules and two carboxylate-oxygens from two cpiap³⁻ ligands. The ligand acts simultaneously as monodentate and tridentate toward Cu^II (1) and Cu^II (2) cations respectively. The lattice water molecules involved in OH···O hydrogen bonding are situated in the void spaces between layers. The zigzag chains, which run along the b-axes further construct three-dimensional metal-organic framework via hydrogen bonding and weak face-to-face π-π interactions. Weak CH···O interactions are also present.     

Synthesis of β-ketoenamine donors having O, N, Se/Te donor functionalities and their reaction chemistry with Pd(II) and Pt(II) metal ions

Monoanionic tridentate ligands LH_a and LH_b containing ONSe and ONTe donor sequences and their Pd²⁺ and Pt²⁺ derivatives were synthesized and characterized. The formation of a five- and a six-membered ring around the central metal atom and associative phenomena in solutions provide extra stability to the metal complexes.     

XPS analysis of the effect of Pt addition to Pd catalysts for complete benzene oxidation

Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

铂-金交替修饰的铂核纳米颗粒的制备与表征

通过吸附在铂纳米颗粒表面的氢交替还原氯金酸和氯铂酸,得到了复合型纳米颗粒Pt@Au/Pt,用UV-Vis光谱、TEM和XRD对其进行了表征.