新型超分子化合物（NH3CH2CH2NH2）3[PW12O40].11H2O晶体的水热合成与表征

首次用水热合成方法报道了超分子化合物（ＮＨ３ＣＨ２ＣＨ２ＮＨ２）３「ＰＷ１２Ｏ４０」．１１Ｈ２Ｏ通过元素分析、ＩＲ光谱、热重分析和Ｘ射线单晶衍射确定了晶体结构,结构分析表明：该晶体属于单斜晶系,Ｐ２１／ｎ空间群,晶胞参数：ａ＝１．８５５９（４）ｎｍ,ｂ＝１．３５１３（３）ｎｍ,ｃ＝２．０４４１（４）ｎｍ,β＝９５．６（３）°,Ｖ＝５．１０３（２）ｎｍ＾３,Ｚ＝４。Ｒ１＝０．０７７５,ｗＲ２＝０．１９５４。     

(C26H40N2O4)[Ln(NO3)5H2O]的合成及其铕缔合物的晶体结构

合成了４个新型的稀土化合物（Ｃ２６Ｈ４０Ｎ２Ｏ４）「Ｌｎ（ＮＯ３）５Ｈ２Ｏ」。采用元素分析和红外光谱表征。用四圆衍射仪测定了（Ｃ２６Ｈ４０Ｎ２Ｏ４）「Ｅｕ（ＮＯ３）５Ｈ２Ｏ」的晶体结构，属三斜晶系，Ｐｉ空间群，晶胞参烤，ａ＝０．９１００（４）ｎｍ，ｂ＝１．３５６（３）ｎｍ，ｃ＝１．６４６３（４）ｎｍ；α＝６８．６２（２）°，β＝７４．８４（３）°，γ＝８７．５０（２）°；Ｚ＝２。中心铕离子由５个硝     

两种具有氢键网络的Ni（Ⅱ）—咪唑配合物的晶体结构和磁性

合成了两种配合物晶体「Ｎｉ（ｉｍ）６」（ＮＯ）３（ＯＨ）（Ｈ２Ｏ）４（Ⅰ）和「Ｎｉ（ｉｍ）４（Ｈ２Ｏ）２」「Ｃ６Ｈ４（ＣＯＯ）２」（（ｉｍ＝Ｃ３Ｈ４Ｎ２）。晶体结构测定表明,晶体（Ⅰ）晶体六方晶系,空间群Ｐ６３／ｍ,ａ＝０．８９９５（１０）ｎｍ,ｃ＝２．１００２（４）ｎｍ,Ｖ＝１．４６８５（４）ｎｍ＾３,Ｚ＝２,Ｒ＝０．０４３,ＲＷ＝０．０４５。晶体（Ⅱ）属单斜晶系,空间群Ｃ２／ｃ,ａ＝２．２２０     

配合物Cu(C14H9NO3)(C3H4N2)的合成、晶体结构及性质研究

合成了配合物Ｃu（Ｃ１４Ｈ９ＮＯ３）（Ｃ３Ｈ４Ｎ２）「Ｃ１４Ｈ９ＮＯ３＾２－为Ｎ －（２－羧基苯基）－水杨醛亚胺,Ｃ３Ｈ４Ｎ２为咪唑」。晶体属正交晶系,空间属Ｐｃａ２１,晶脓包 参数a＝０．９４４５３（１２）ｎｍ,b＝１．１２２７８（９）ｎｍ,ｃ＝２．９１２３（４）ｎｍ,Ｖ＝３．０８８５（６）ｎｍ＾３,Ｍｒ＝３７０．８４,Ｚ＝８,最终的偏离因子Ｒ＝０．０３６,ｗＲ＝０．０８７,ＧＯＦ＝０．９７５,三齿     

（Y（NTO）2NO3（H2O）5）.2H2O的制备,晶体结构和热分解机理的…

合在了（Ｙ（ＮＴＯ）２ＮＯ３（Ｈ２Ｏ）５）．２Ｈ２Ｏ（ＮＴＯ为３－硝基－１，２，４－三唑－５－酮）并测定了晶体结构，晶体属单斜晶系，空间群Ｃｍ，晶胞参数：ａ＝０．６７７３（２）ｎｍ，ｂ＝２．０８６６（２）ｎｍ，ｃ＝０．６５５１（１）ｎｍ；β＝１０２．９８（２）°Ｖ＝０．９０２１（１）ｎｍ＾３，Ｚ＝２，Ｄｃ＝１．９７０ｇ．ｃｍ＾－３，μ＝３３．４９ｃｍ＾－１，Ｆ（０００）＝５４０，Ｒ＝０．０３２，中     

Ln(NO_3)_3·C_(26)H_(38)N_2O_4(Ln=La、Ce)配合物的合成和La(NO_3)_3·C_(26)H_(38)N_2O_4·CH_3CN的晶体结构

合成了２个新的希土冠醚配合物Ｌｎ（ＮＯ３）３·Ｃ２６Ｈ３８Ｎ２Ｏ４（Ｌｎ＝Ｌａ、Ｃｅ；Ｃ２６Ｈ３８Ｎ２Ｏ４＝１，７，１０，１６－四氧－４，１３－二氮杂－Ｎ，Ｎ′－二苄基环十八烷）。通过元素分析，红外光谱，拉曼光谱及其１Ｈ核磁共振谱进行表征。用四圆衍射仪测定了Ｌａ（ＮＯ３）３·Ｃ２６Ｈ３８Ｎ２Ｏ４·ＣＨ３ＣＮ的晶体结构。晶体属三斜晶系，Ｐ１空间群，晶胞参数：ａ＝１．２８６９（４）ｎｍ，ｂ＝１．５８６８（６）ｎｍ，ｃ＝０．９１４７（２）ｎｍ；α＝１０１．８９（２）°，β＝１０５．３８（２）°，γ＝７１．９６（３）°；Ｚ＝２。ｄｃａｌｄ．＝１．５８ｇ·ｃｍ－３，μ（ＭｏＫα）＝１３．２５ｃｍ－１。中心镧离子与冠醚配体中的４个氧原子和２个氮原子配位，３个硝酸根中的６个氧原子也与Ｌａ３＋配位，形成配位数为１２的配合物。     

[（C5H4CH3）2HoN4cpH]2.[（C5H4CH3）（C5H5）HoN4CPh]2的合成和晶体结构2

（Ｃ５Ｈ４ＣＨ３）３Ｈｏ和（Ｃ５Ｈ４ＣＨ３）２Ｈｏ（Ｃ５Ｈ５）与５－本基四唑在ＴＨＦ中反应，得到了复合产物「（Ｃ５Ｈ４ＣＨ３）２ＨｏＮ４ＣＰｈ」２．「（Ｃ５Ｈ４ＣＨ３）（Ｃ５Ｈ５）ＨｏＮ４ＣＰｈ」２，该晶体属三斜晶系，Ｐ１空间群，晶胞参数为ａ＝９．３８６（３），ｂ＝１３．０７１（３），ｃ＝１６．５７１（２）Ａ，α＝８６．９０（１），β＝７４．６１（２），γ＝７７．３０（２）°，Ｖ＝１９１２．８（８     

［La（EO_3）_3（H_2O）］（ClO_4）_3·H_2O的晶体结构

稀土高氯酸盐开环冠醚三缩乙二醇（ＥＯ_３）［Ｌａ（Ｃ_６Ｈ_（１４）Ｏ_４）_３（Ｈ_２Ｏ）］（ＣｌＯ_４）_３·Ｈ_２Ｏ，单斜晶系，Ｐ２_１／ｃ空间群。晶胞参数为：ａ＝１５．４７４（２），ｂ＝１１．３８６（１），ｃ＝２０．８４１（４），β＝９９．８２（１）°，Ｖ＝３６１８（１），ＭｏＫα，Ｚ＝４，Ｄ_ｃ＝１．７１８ｇ／ｃｍ３，μ＝１．４９９ｍｍ￣（－１）。全矩阵最小二乘精细修正，结构因子Ｒ＝０．０５６，Ｒ_ｗ＝０．０８３。中心原子Ｌａ与开环冠醚醚链上的Ｏ（１）～Ｏ（９）及一个水分子形成１０配位双帽四方反棱柱结构。弱配体高氯酸根不参加配位。     

（n—C4H9）4N2（OC14H8O2）Mo4O10（OCH3）2的合成和晶体结构

为探讨钼多酸根阴离子在有机化学反应中的催化机理，用菲醌作底物合成了（ｎ－Ｃ４Ｈ９）４Ｎ）２（ＯＣ１４Ｈ８Ｏ）２Ｍｏ４Ｏ１０Ｏ１０（ＯＣＨ３）２）配合物，Ｘ射线单晶结构分析表明，该晶体属单斜晶系，空间群Ｐ２１／ｃ，ａ＝１．３１４９（５）ｎｍ，ｂ＝１．８６６６（８）ｎｍ，ｃ＝１．８９０３（３）ｎｍ，β＝１０４．０６（３）Ｚ＝２．收集到独立衍射点３５０５个，其中１３８２个为可观测点，最终一致性因子Ｒ＝０     

［Cu_2（C_6H_5COO）_4（C_3H_4N_2S）_2］的合成、晶体结

在２－氨基噻唑存在下，利用铜粉和过氧化苯甲酰的氧比加成反应，在丙酮中合成了双核铜（Ⅱ）配合物［Ｃｕ_２（Ｃ_６Ｈ_５ＣＯＯ）_４（Ｃ_３Ｈ_４Ｎ_２Ｓ）２］．晶体属单斜晶系，Ｐ２１／ｎ空间群，晶胞参数：ａ＝１．０６８５（１）ｎｍ，ｂ＝１．９０２８（６）ｎｍ，ｃ＝１．７０４６（９）ｎｍ；α＝γ＝９０°，β＝９６．４９（３）°，Ｖ＝３．４４３（４）ｎｍ~３，Ｚ＝４．Ｆ（０００）＝８２４，Ｄｃ＝１．５５５８ｇ／ｃｍ~３，μ＝１４．０７８ｃｍ~（－１），最终偏离因子Ｒ＝０．０４８２１，Ｒｗ＝０．０５３１４．通过元素分析、ＩＲ、ＴＧ、Ｘ射线粉末衍射表征了配合物的结构．     

Ln4(CH2)4 cubane-type rare-earth methylidene complexes consisting of "(C5Me4SiMe3)LnCH2" units (Ln = Tm, Lu)

Tetranuclear cubane-type rare-earth methylidene complexes consisting of four "Cp'LnCH(2)" units, [Cp'Ln(μ(3)-CH(2))](4) (4-Ln; Ln = Tm, Lu; Cp' = C(5)Me(4)SiMe(3)), have been obtained for the first time through CH(4) elimination from the well-defined polymethyl complexes [Cp'Ln(μ(2)-CH(3))(2)](3) (2-Ln) or mixed methyl/methylidene precursors such as [Cp'(3)Ln(3)(μ(2)-Me)(3)(μ(3)-Me)(μ(3)-CH(2))] (3-Ln). The reaction of the methylidene complex 4-Lu with benzophenone leads to C═O bond cleavage and C═C bond formation to give the cubane-type oxo complex [Cp'Lu(μ(3)-O)](4) and CH(2)═CPh(2), while the methyl/methylidene complex 3-Tm undergoes sequential methylidene addition to the C═O group and ortho C-H activation of the two phenyl groups of benzophenone to afford the bis(benzo-1,2-diyl)ethoxy-chelated trinuclear complex [Cp'(3)Tm(3)(μ(2)-Me)(3){(C(6)H(4))(2)C(O)Me}] (6-Tm).     

Synthesis and thermal decomposition of CH3NH3Ln(SO4)2.4H2O (Ln=Tm,Yb OR Lu)

The double sulfates of Tm, Yb and Lu with monomethylammonium were obtained by evaporation of an aqueous mixture of rare earths(III) sulfate and monomethylammonium sulfate at room temperature and treatment of the concentrated mixture with ethanol. After identification of the double sulfates, they were examined by means of TG, DTG and DTA analysis, from 20 to 700°. Two clearly separated stages of thermal decomposition were evident. It was possible to determine the stoichiometry of the obtained compounds from the TG curves.

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Zusammenfassung Die Doppelsulfate von Tm,Yb und Lu mit Monomethylammonium wurden durch Verdampfen eines wäßrigen Gemisches aus Seltenerden(III)-sulfaten und Monomethylammoniumsulfate bei Raumtemperatur und durch Behandlung des konzentrierten Gemisches mit Ethanol erhalten. Nach Identifizierung der Doppelsulfate wurden diese im Temperaturbereich 20–700° mittels TG, DTG und DTA- Analyse untersucht. Zwei eindeutig separate thermische Zersetzungsschritte wurden deutlich. Anhand der TG-Kurven war eine Bestimmung der Stöchiometrie der erhaltenen Verbindungen möglich.

     

Zur solvensfreien Darstellung von Tetramethylammoniumsalzen: Synthese und Charakterisierung von [N(CH3)4]2[C2O4], [N(CH3)4][CO3(CH3)], [N(CH3)4][NO2], [N(CH3)4][CO2H] und [N(CH3)4][O2C(CH2)2CO2(CH3)]

Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH₃)₄]₂[C₂O₄], [N(CH₃)₄][CO₃CH₃], [N(CH₃)₄][NO₂], [N(CH₃)₄][CO₂H], and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH₃)₄]₂[C₂O₄] (cubic; a = 1 114.8(3) pm), [N(CH₃)₄][CO₃CH₃] (P2₁/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH₃)₄][NO₂] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH₃)₄][CO₂H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] (P2₁; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.     

Dimethylarsenazid (CH3)2AsN3, Dimethylwismutazid (CH3)2BiN3 und Dimethylthalliumzid (CH3)2TiN3

The reaction of (CH₃)₂AsJ and AgN₃ yields (CH₃)₂AsN₃; a colourless liquid (b. p. 136°C) which dissolves as a monomeric in benzene. (CH₃)₂BiN₃ is precipitated in form of colourless needles (dec. temp. 150°C) from an etherical solution of Bi(CH₃)₃ and HN₃. According to its vibrational and mass spectra the molecules are not associated although the (CH₃)₂BiN₃ is not soluble; dipole association of this polar molecules is assumed for the crystal structure. (CH₃)₂TlN₃ can be obtained from TI(CH₃)₃ and ClN₃ as well as from (CH₃)₂TlOH and HN₃ in form of colourless needles and leaves (dec. temp. 245°C). According to its vibrational spectra it has an ionic structure, (CH₃? Tl? CH₃)⁺N^?₃.     

Thermal decomposition of di-t-butyl peroxide in the presence of (CH3)2CCH2: Reactions of CH3, (CH3)2ĊCH2CH3, and (CH3)2ĊCH2C(CH3)2CH2CH3 radicals

A study of the reaction initiated by the thermal decomposition of di-t-butyl peroxide (DTBP) in the presence of (CH₃)₂C?CH₂ (B) at 391–444 K has yielded kinetic data on a number of reactions involving CH₃ (M·), (CH₃)₂CCH₂CH₃ (MB·) and (CH₃)₂?CH₂C(CH₃)₂CH₂CH₃ (MBB·) radicals. The cross-combination ratio for M· and MB· radicals, rate constants for the addition to B of M· and MB· radicals relative to those for their recombination reactions, and rate constants for the decomposition of DTBP, have been determined. The values are, respectively, where θ = RT ln 10 and the units are dm^3/2 mol^?1/2 s^?1/2 for k₂/k and k₉/k, s^?1 for k₀, and kJ mol^?1 for E. Various disproportionation-combination ratios involving M·, MB·, and MBB· radicals have been evaluated. The values obtained are: Δ₁(M·, MB·) = 0.79 ± 0.35, Δ₁(MB·, MB·) = 3.0 ± 1.0, Δ₁(MBB·, MB·) = 0.7 ± 0.4, Δ₁(M·, MBB·) = 4.1 ± 1.0, Δ₁(MB·, MBB·) = 6.2 ± 1.4, and Δ₁(MBB·, MBB·) = 3.9 ± 2.3, where Δ₁ refers to H-abstraction from the CH₃ group adjacent to the center of the second radical, yielding a 1-olefin. © 1994 John Wiley & Sons, Inc.     

Mass spectra of polymeric thioformaldehydes (CH2S)3, (CH2S)4, (CH2S)5 and (CH2S)x

The mass spectral fragmentations of various thioformaldehydes, 1,3,5-trithiacyclohexane, 1,3,5,7-tetrathiacyclooctane, 1,3,5,7,9-pentathiacyclodecane and a polymeric form (CH₂S)_x have been examined. The principal features of the spectra are reported. The fragmentation occurred by fracture of the ring in the cyclic compounds with or without rearrangement.     

Crystal structure investigation of ternary molybdates Li3Ba2Ln3(MoO4)3 (Ln=Gd,Tm)

Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Physics, Siberian Branch, Russian Academy of Sciences. Buryat Institute of Natural Sciences, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 3, pp. 126–130, May–June, 1992.     

Self-assembly of the octanuclear cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ and the one-dimensional N-propylcarbamate-linked coordination polymer {[Cu(O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n

The reaction of Cu(ClO4)2.6-H2O and n-propylamine in methanol gives two high-nuclearity products of well-defined compositions. At amine concentrations greater than seven equivalents compared to copper ion concentration, the system fixes carbon dioxide from air to form the one-dimensional carbamate-bridged coordination polymer, {[Cu(mu2-O,O'-O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n ({1-ClO4}n). Lower relative amine concentrations lead to the self-assembly of an octanuclear copper-amine-hydroxide cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ (2). Both compounds exhibit unique structures: {1-ClO4}n is the first mu2-O,O'-mono-N-alkylcarbamate-linked coordination polymer and 2 is the largest copper-hydroxide-monodentate amine cluster identified to date. The crystal structures indicate that the size of the n-propyl group is probably crucial for directing the formation of these compounds. Magnetic susceptibility studies indicate very weak antiferromagnetic coupling for 1. The octanuclear cluster 2 displays slightly stronger net antiferromagnetic coupling, despite the presence of a number of Cu-O(H)-Cu angles below the value of about 97 degrees that would normally be expected to yield ferromagnetic coupling.