Mikromengen Chlorid (10?6 bis 10?5 m)

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Geringe Eisenspuren von 10?7 bis 10?6% in Salzs?ure und in Flu?s?ure

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12,52-二羟基-15,55-二甲基-14,16,34,36,54,56,74,76-八硝基-2,4,6,8-四氧桥连-1,3,5,7（1,3）-杯[4]芳烃的合成

以1,5-二氟-2,4-二硝基苯和3,4,5-三甲氧基甲苯为起始原料,经环化、甲基化、硝化和去甲基化反应,合成了一种新型杯芳烃衍生物,其结构经¹H NMR,¹³C NMR,¹⁵N NMR和元素分析表征。      

Die Bestimmung von Kupferspuren bis herab zu 10?6% in Reinaluminium und Reinindium mit Nickeldi?thyldithiophosphat

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Ein Coulometer zur Messung kleiner Strommengen von 10?2 bis 10?5 C

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Zur Analyse von 10?6 bis 10?9m L?sungen von Metallen

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Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb] 2+ [PtCl6]2?, [Ph4Sb]+[AuCl4]?, and [Ph4Sb] 2+ [SnCl6]2?: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph₄Sb]⁺ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.     

Die halbquantitative Bestimmung von Cl?, Br?, J?, SCN?, AsO43?, Cr2O72? und [Fe(CN)6]3?

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Spuren von Jod (10? %) in Silicium als Halbleitermaterial

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13C NMR spectra of coordinated propargyl cations [Cp2Mo2(CO)4(μ-η2,η3-(HC≡CCR1R2)]+ BF4/?

A strong deshielding effect is observed for the carbon signal of carbocation center (C⁺) in the ¹³C NMR spectra of coordinated propargyl cations [Cp₂Mo₂(CO)₄(μ-η²,η³-(HC≡CCR¹R²)]⁺ BF₄⁻ (R¹ = R² = H) 1, (R¹ = Me, R² = H) 2, and (R¹ = R² = Me) 3 when hydrogen is replaced by methyl; the effect increases with the Mo-C⁺ distance (75.37, 98.3, and 148.68 ppm for compounds 1, 2, and 3, respectively). This indicates that the back-donation of electron density from the metal onto the ligand makes a substantial contribution to the stabilization of these cations. Original Russian Text ? I.V. Barinov, V.A. Chertkov, 2009, published in Vestnik Moskovskogo Universiteta. Khimiya, 2009, No. 1, pp. 29–34.     

Phosphonium salts [Ph3AlkP] 2+ [Hg2I6]2? and [Ph3AlkP] 2+ [Hg4I10]2?: Synthesis and structure

Mercury complexes [Ph₃AlkP]₂⁺[Hg₂I₆]²⁻ and [Ph₃AlkP]₂⁺[Hg₄I₁₀]²⁻ (R = Me, Et, Pr, iso-Pr, Bu, iso-Bu) are synthesized by the reactions of triphenylalkylphosphonium Ph₃AlkPI with mercury iodide in acetone with the mole ratio 1: 1 and 1: 2, respectively. According to X-ray diffraction data, the phosphorus atom in the cations of the [Ph₃(iso-Pr)P]₂⁺[Hg₂I₆]²⁻, [Ph₃BuP]₂⁺[Hg₂I₆]²⁻, and [Ph₃(iso-Pr)P]₂⁺[Hg₄I₁₀]²⁻ complexes has a distorted tetrahedral coordination. The CPC bond angles and P-C bond lengths vary within 107.3(4)°-112.0(4)° and 1.774(8)-1.827(7) ?. In the [Hg₂I₆]²⁻ centrosymmetric binuclear anions, the mercury atoms of tetrahedral coordination lie in two near-perpendicular Hg₂I₆planes. Hg₄I₄ eight-membered cycles of the [Hg₄I₁₀]²⁻ tetranuclear anion are joined into polymeric chains through Hg … I coordination bonds (3.334, 3.681 &OA) due to which Hg atoms have a trigonal bipyramidal coordination. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, N.N. Klepikov, O.K. Sharutina, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 267–273.     

Unusual ion UO4? formed upon collision induced dissociation of [UO2(NO3)3]?, [UO2(ClO4)3]?, [UO2(CH3COO)3]? ions

The following ions [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ were generated from respective salts (UO₂(NO₃)₂, UO₂(ClO₄)₃, UO₂(CH3COO)2) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO₄ ⁻ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U^VI compound, in which oxygen atoms bear unpaired electron and negative charge.     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

Synthesis and structure of cobalt complexes [Ph3(n-Pr)P 2+ [CoI4]2? and [Ph3(n-Am)P 2+ [CoI4]2?

Complexes Ph₃(n-Pr)P₂⁺[CoI₄]²⁻ (I) and [Ph₃(n-Am)P]₂⁺ [CoI₄]²⁻ (II) were synthesized by reactions of triphenyl(alkyl)phosphonium iodide with cobalt(II) iodide in acetone. According to the X-ray diffraction data, complexes I and II consist of tetrahedral triphenyl(alkyl)phosphonium cations (for I, P-C is 1.787(4)–1.804(4) ? and CPC is 106.73(18)°–111.4(18)°; for II P-C is 1.786(6)–1.802(6) ? and CPC is 107.6(3)°–111.7(3)°) and [CoI₄]²⁻ anions (Co-I 2.5923(6)–2.6189(6) ?, ICoI 101.86(2)°–113.25(2)° for I; Co-I 2.5899(9)–2.6171(9) 107.01(3)°–110.47(3)° for II).     

[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物[Pt₂(P₂O₄H₂)₄]^4-和[Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。     

Synthesis and crystal structure of π-complex of copper(I) with 1-allylbenzimidazolium cation [C7H5N2H(C3H5)]+ [Cu3Cl4]?

Single crystals of [C₇H₅N₂H(C₃H₅)]⁺[Cu₃Cl₄]^– were obtained for the first time by ac electrochemical synthesis from 1-allylbenzimidazolium and copper(II) chlorides in ethanol and structurally characterized. The unit cell parameters are a=8.6755(9) , b=8.846(1) , c=10.4540(7) , =85.36(1)°, =70.529(7)°, =83.29(1)° , V=750.5(3) ³, space group P , R(F)=0.0551. In the -complex, the copper and chlorine atoms form complicated infinite chains along the x axis. The 1-allylbenzimidazolium cation functions as an original bridge: it is coordinated by the Cu atom of one cuprous-chloride chain through the C=C bond of the allyl group and forms a N-HCl hydrogen bond with another inorganic chain through the N atom of the imidazole ring. The trigonal pyramidal environment of the Cu(1) atom includes three Cl atoms and the C=C bond; the environments of the Cu(2), Cu(3), and Cu(3a) are composed only of chlorine atoms. The positions of the Cu(2) and Cu(3a) atoms are partially disordered, which is manifested by the high thermal parameters for the Cu(2) atom and by the splitting of another copper atom into two equally occupied positions Cu(3) and Cu(3a).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 199–203.Original Russian Text Copyright © 2005 by Goreshnik, Schollmeyer, Myskiv.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

离子化合物[2，6-bis(Benzimidazol-2-yl)pyridineH2]2+·[SbCl5]2-的合成、晶体结构及荧光性质

利用邻苯二胺、2,6-吡啶二甲酸与三氯化锑在盐酸溶液中经水热反应,合成了一种新的离子型化合物[2,6-bis(Benzimidazol-2-yl)pyridineH₂]²⁺·[SbCl₅]^2-。通过化学分析、元素分析、热重分析、红外光谱及荧光光谱对结构和性质进行了表征,用X-射线单晶衍射测定了该化合物的晶体结构。化合物的晶体属三斜晶系,P1空间群。Sb³⁺与其周围5个氯离子配位,构成一个畸变四方锥构型[SbCl₅]^2-配位结构,2个配阴离子[SbCl₅]^2-之间通过Sb(1)…Cl(1)^ⅱ次级键形成四元环状结构,并与2,6-二(苯并咪唑-2′)吡啶两价阳离子,通过离子键及氢键形成三维网状离子化合物晶体。该化合物具有很好的荧光特性。     

双核Fe配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2的合成和晶体结构

由侧链带有噻吩的环戊二烯基配体C5H5C6H10C4H3S与Fe(CO)5在二甲苯中加热回流,合成了1个新颖的四羰基二铁配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2。通过元素分析、IR、1H NMR对其结构进行了表征,用X-射线单晶衍射确定了其结构。X-射线单晶衍射表明配合物中有2个桥羰基和2个端羰基,Fe-Fe的键长为0.25465(10)nm。     

Molecular and crystal structures of [FeCl(HMPA)3(H2O)2]2+(FeCl4) 2? · 3HMPA

IR and single-crystal X-ray diffraction study are carried out for compound, C₃₆H₁₁₂Cl₉Fe₃N₁₈O₈P₆(I). It crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 14.2992(3), b = 21.4351(4), c = 25.5407(5) ?, V = 7828.3(3) ?³, ρ_calcd = 1.553 g/cm³, Z = 4. The FeCl fragment is coordinated with chlorine atom of two water molecules and three HMPA molecules to form a cation, with a distorted octahedral coordinate geometry. In the crystal I, the cation is linked with HMPA by the O-H…O hydrogen bond. The chiral crystal is formed through self-assembly even from achiral molecules.