Synthesis of Tricyclic (λ5)-Phosphoranes; unusual N-demethylation/N-alkylation reactions during the oxidative addition of hexafluoroacetone and tetrachloro-ortho-benzoquinone to benzodiaza-λ3-phosphorinones. Single crystal X-ray diffraction studies of various products

The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N′-methylanthranilamide derivatives 2 – 4 . Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 5 – 7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 8 – 10 and 12 . With 2-chloroethylammonium chloride/triethyl-amine the P? NHCH₂CH₂Cl-substituted compound 11 was obtained from the P^IIICl-species 6 . The reaction of 8 – 10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH₂CH₂Cl groups was found to alkylate the CH₃N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13 – 16 . The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a λ⁵-oxazaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18 – 20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16 , and for the precursor compound 9 . The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14 : the (λ⁵)-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the λ³P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms.     

Kristallstruktur des „supramolekularen”︁ Komplexes [Cs2(18-Krone-6)][HgI4] mit ungewöhnlich koordinierten Cs-Ionen

Crystal Structure of the “Supramolecular” Complex [Cs₂(18-crown-6)][HgI₄] with Unusually Coordinated Cs Ions The reaction of 18-crown-6, 1,4,7,10,13,16-hexaoxacyclooctadecane, with HgI₂/CsI in methanol yields crystals of [Cs₂(C₁₂H₂₄O₆)][HgI₄]. The compound crystallizes monoclinically, space group P2₁/c, Z = 4, a = 1574.8(3), b = 1067.0(3), c = 1693.2(6) pm, and β = 98.29(3)º. The structure consists of a network made up of two different types of [Cs-(18-crown-6)-Cs]²⁺ cations, interconnected by [HgI₄]^2? anions. The cations form an “anti-sandwich” structure with relatively short Cs ? Cs distances of 382 pm in the first type of cations and a longer distance of 480 pm in the second type of cations.     

Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.     

Single polymer molecules adsorbed to mica and the oppositely charged polymer/surfactant complexes formed at the air–water interface visualized by atomic force microscopy

In the present study, the structure and morphology of single sodium poly(styrenesulfonate) (PSS) molecules adsorbed to mica surface from the natural aqueous solution is investigated using atomic force microscopy technique. Results show that single PSS molecules are observed which show a morphology of wormlike coils. Meanwhile, single sodium poly(styrenesulfonate) (PSS)/Hexadecyltrimethylammonium bromide (CTAB) complexes deposited on mica from the air–water interface are also observed. However, the PSS/CTA⁺ complexes show different conformations by appearing in the morphology of circular patches. Experimental data are in fair agreement with the theoretical analysis.     

Synthesis and structure of a bowl-like molecule by threefold metathesis reactions

A bowl-like molecule was designed and efficiently synthesized by threefold metathesis reactions, and its structure was determined by NMR, MALDI-TOF MS spectrum, and X-ray crystallographic analysis.     

变频空调制冷系统流量调节性能分析和实验研究

通过实验分析不同膨胀阀开度和压缩机频率下系统性能。过热度在‘0’点及前后情况下,制冷系统性能及回油状况随膨胀阀开度调节,会出现较大变化。且在过热度为‘0’时系统制冷量和能效比最高。同时对不同频率下系统性能参数变化规律尤其是换热器效率影响进行分析。给出膨胀阀开度和压缩机变转速联合调节在系统性能最优状态下调节策略。     

Indium distribution and light emission in wurtzite InGaN alloys: Several-atom In-N clusters

Considering various In distributions, we investigate electronic structures and light emission of wurtzite In_xGa_1 − xN (0?x?1) alloys. We find In_xGa_1 − xN forms a random alloy, in which many several-atom In-N clusters and short In-N- chains can exist. Small In-N clusters, especially in-plane ones, strongly localize valence electrons and dominate light emission in Ga-rich In_xGa_1 − xN alloys, which is consistent with experiments.     

根据计算结构因子重新指定镍(II)8-羟基喹啉的两个络合物(英文)

晶体学研究曾认为分子式是NaNiQ2HQCLO4的结构并不含有钠而应为H3ONiQCLO4.相似地,稀土-Ni络合物YQHQ2NiQ3CLO4也不含有钇而应为H3ONi2Q3CLO4.晶体结构描述的修正系根据文献报导的原子坐标计算结构因子所导出的结果.     

Common properties of table algebras and association schemes

The concept of table algebra in the title is a real nonsingular generalized table algebra in the sense of [Z. Arad, E. Fisman, M. Muzychuk, Generalized table algebras, Israel J. Math. 114 (1999) 29–60]. In this paper we first give some definitions and facts about table algebras. It is well known that every association scheme gives a Hecke-algebra which is a table algebra too. This leads to the natural question which properties of association schemes stay valid for table algebras. For instance, we prove the Second Isomorphism Theorem and the Jordan–Holder's theorem for standard table algebras.     

Polarized structure functions of nucleons and nuclei

We determine the quark distributions and structure functions for both unpolarized and polarized DIS of leptons on nucleons and nuclei. The scalar and vector mean fields in the nucleus modify the motions of the quarks inside the nucleons. By taking into account this medium modification, we are able to reproduce the experimental data on the unpolarized EMC effect, and to make predictions for the polarized EMC effect. We discuss examples of nuclei where the polarized EMC effect could be measured. We finally present an extension of our model to describe fragmentation functions.