3-硝基-1,2,4-三唑-5-酮镱配合物的制备及其晶体结构

３硝基１，２，４三唑５酮（ＮＴＯ）的锂盐水溶液与Ｙｂ２Ｏ３的稀硝酸溶液反应，制备了标题配合物，其化学式为Ｙｂ（ＮＴＯ）３·１０Ｈ２Ｏ。用Ｘ射线衍射法测定配合物的晶体结构，其分子式为［Ｙｂ（ＮＴＯ）３（Ｈ２Ｏ）４］·６Ｈ２Ｏ。属单斜晶系，空间群为Ｃ２／ｃ。晶胞参数如下：ａ＝３６９３１（５）ｎｍ，ｂ＝０６６８３（１０）ｎｍ，ｃ＝２５６５６（３）ｎｍ，β＝１３０９７４（５）°，Ｖ＝４７８１１（１１）ｎｍ３，Ｚ＝８，Ｄｃ＝２０１３ｇ·ｃｍ－３，μ＝４０１７ｍｍ－１，Ｆ（０００）＝２８５０。镱离子的配位数为７，其配位多面体为五角双锥。     

一经式异构体[Co(N-(3-Aminopropyl)-1,3-propanediamine)(1,2-diamino-2-methylpropane)Cl][ZnCl4]·2H2O的合成及晶体结构

用过氧化物法合成了新体系［ Ｃｏ（ ３, ３－ｔｒｉ）（ ｉｂｎ） ＣＩ］［ ＺｎＣｌ４］（ ３, ３－ｔｒｉ＝ Ｎ－（ ３－Ａｍｉｎｏｐｒｏｐｙｌ）－ １, ３－ｐｒｏｐａｎｅｄｉａ－ｍｉｎｅ; ｉｂｎ＝１, ２－ｄｉａｍｉｎｏ－２－ｍｅｔｈｙｌｐｒｏｐａｎｅ）中的一经式异构体［Ｃｏ（３, ３ｔｒｉ）（ｉｂｎ）ＣＩ］［ＺｎＣｌ４］·２Ｈ２Ｏ,解析了其晶体结构。晶体学参数：三斜晶系,空间群Ｐ１（＃２）,ａ＝９９．５８（２）ｎｍ,ｂ＝１１４．８３（２）ｎｍ,ｃ＝９８．８１（１）ｎｍ,ａ＝９６．７９（２）°,β＝９７．２４３（１０）°,ｙ＝９６．８９（１）°,Ｖ＝１．１０５５（３）Ｘ １０６ｎｍ３,Ｄｅ＝１．６７８ｇ·ｃｍ－３,Ｚ＝２,Ｆ０００＝５７２．００,μ（ Ｍｏ Ｋａ）＝ ２４． ５９ｃｍ－１, Ｒ＝ ０． ０２５, Ｒｗ＝ ０． ０３４。晶胞中含 ２个配位阳离子, ２个 ［ＺｎＣｌ４］２－阴离子及 ４个水分子。     

α,ω-双(4-(4′-甲基)-偶氮苯基)苯氧甲基-1,1,3,3-四甲基二硅氧烷的合成和结构

合成了（ＣＨ３（Ｃ６Ｈ４）Ｎ２（Ｃ６Ｈ４）ＯＣＨ２Ｓｉ（ＣＨ３）２２Ｏ,对其晶体结构及分子偶极矩进行了研究．结果表明,晶体属单斜晶系,Ｉ２Ａ空间群,晶胞参数如下：ａ＝２．１７８３４ｎｍ,ｂ＝０．８０３２５ｎｍ,ｃ＝２．０８８９５ｎｍ,β＝１１９．１９１°,Ｖ＝３１８２６ｎｍ３,Ｚ＝４,Ｄｃ＝１．２１６ｋｇ／ｍ３．分子偶极矩μ＝８．９３２×１０－３０Ｃ·ｍ．通过对分子结构和矩值的分析,说明了由刚性基团和柔性基团组成的端介晶基四甲基二硅氧烷的性能与结构之间的关系．     

三维氢键超分子化合物[H3cth][Fe(CN)6]·3H2O的合成与结构

用内消旋５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四烷（ｃｔｈ）和Ｋ_３［Ｆｅ（ＣＮ）_６〕合成了氢键连接的超分子化合物［Ｈ_３ｃｔｈ］［Ｆｅ（ＣＮ）_３］·３Ｈ_２Ｏ．该化合物的晶体属三斜晶系，Ｐ－１空间群，晶胞参数ａ＝０．９３０ ９７（９）ｎｍ，ｂ＝１．０５１ ６０（１１）ｎｍ，ｃ＝１．６３８ ４７（１７）ｎｍ，ａ＝１０１．０７７（２）°，β＝９０．８６０（２）°，γ＝１１１．６７１（２）°， Ｖ＝１．４５６ ４（３） ｎｍ３， Ｚ＝２， Ｒ＝０．０４１５．晶体中质子化的大环四胺与六氰合铁（Ⅱ ）离子之间通过氢键连接成二维层状结构，而水分子所形成的氢键使化合物呈现三维超分子网络．     

Mn（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物的合成及结构

合成了４种锰（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物：Ｍｎ（ｂｚａｃｅｎ）ＬＣｌＯ＿４．（Ｌ为哌嗪，吡啶，γ－甲基吡啶和乙腈），测定了配合物［Ｍｎ（ｂｚａｃｅｎ）（ＣＨ＿（３）ＣＮ）ＣｌＯ＿４］的结构．晶体属正交晶系．空间群Ｐ＿ｎｍａ．晶胞参数：ａ＝０．９０７７（１）ｎｍ，ｂ＝１．５５６３（１）ｎｍ，ｃ＝１．７２０５（２）ｎｍ，Ｖ＝２．４３０５ｎｍ￣３，Ｚ＝４，Ｄ＿ｃ＝１．４８ｇ／ｃｍ￣３，Ｄ＿ｍ＝１．４９ｇ／ｃｍ￣３．配合物呈拉长八面体结构．对配合物的电子光谱和红外光谱进行了归属．     

（四甲基二硅撑）二（3－三甲硅基环戊二烯基）四羰基二铁及其相关化合物的合成及结构

１，２－二（三甲硅基环戊二烯基）四甲基二硅烷与Ｆｅ（ＣＯ）_５在二甲苯中于１０５～１１０℃反应除分离到少量标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（５）外，主要是生成了脱Ｍｅ_３Ｓｉ基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（１）及１的热重排异构体［Ｍｅ_２ＳｉＣ５Ｈ４－Ｆｅ（ＣＯ）_２］_２（２）．将５的二甲苯溶液加热回流１８ｈ，则转化为其异构体［Ｍｅ_２Ｓｉ（Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２（６）．脱硅基发生在由相应反应物制备５的过程中。且脱硅基是与反应物中（Ｍｅ_２ＳｉＳｉＭｅ_２）桥的存在有关．５的晶体结构经Ｘ射线衍射测定属单斜晶系，Ｐ２_１／ｍ空间群，晶体学数据：ａ＝０．６７８０（１）ｎｍ，ｂ＝２．２３０３（９）ｎｍ，ｃ＝０．９９８８（１）ｎｎ，；β＝９８．９６（１）°，Ｖ＝１．４９６０ｎｍ~３．Ｚ＝２，Ｄ_ｃ＝１．３６ｇ／ｃｍ~３．     

［Mn_2（bzacen）_2（MeOH）_2（μ－4，4′－bipy）］（ClO_4）_2的合成、结构和谱学性质

合成了［Ｍｎ_２（ｂｚａｃｅｎ）_２（ＭｅＯＨ）_２（μ－４，４′－ｂｉｐｙ）］（ＣｌＯ_４）_２化合物，并测定其晶体结构。该晶体属单斜晶系，空间群Ｐ２_１／ｎ，晶胞参数：ａ＝１．３０８２（３）ｎｍ，ｂ＝１．２７１３（３）ｎｍ，ｃ＝１．８００６（５）ｎｍ，β＝１１０．９１（２）°，Ｚ＝２，μ＝５．９７ｃｍ－１，Ｒ＝０．０５８０，ＧＯＦ＝１．６６．在配合物阳离子中，４，４′－联吡啶桥联２个［Ｍｎ（ｂｚａｃｅｎ）（ＭｅＯＨ）］＋，而锰原子具有３个Ｎ原子和３个Ｏ原子形成的扭曲八面体配位构型。红外光谱和拉曼光谱均表明，形成配合物后，ｖ_（Ｃ＝Ｎ）、ｖ（Ｃ＝Ｏ）、和ｖ（Ｃ＝Ｃ）移向低频。红外光谱的１１１０ｃｍ￣（－１）谱带表明ＣｌＯ_４￣－未与Ｍｎ（Ⅲ）配位，８１２ｃｍ￣（－１）振动说明４，４′－ｂｉｐｙ充当桥联二齿配体。拉曼光谱中的４６３ｃｍ￣（－１）和４０１ｃｍ￣（－１）别为Ｍｎ－Ｏ和Ｍｎ－Ｎ的振动带。电子光谱证明存在ｄ－ｄ、ｄ－π和π－π跃迁。电极电位测定显示该配合物Ｍｎ（Ⅲ）的价态是稳定的。     

含硫、氮Schiff碱配合物—二水二分之一二甲基亚砜醋酸四邻香草醛缩胺基硫脲合镉（Ⅱ）的合成及晶体结构

Ｘ射线单晶衍射结果表明，三核镉配合物Ｃｄ３［ＣＨ３Ｏ（Ｏ）Ｃ６Ｈ３ＣＨ＝ＮＮＨＣ（Ｓ）ＮＨ２］４·［ＣＨ３ＣＯＯ］２·１／２［ＣＨ３Ｓ（Ｏ）ＣＨ３］·２Ｈ２Ｏ为单斜晶系，空间群为Ｃ２／ｃ，ａ＝３．４２１４（４），ｂ＝１．１５８１（２），ｃ＝１．７９３２（５）ｎｍ，β＝１１９．７６（１）°，Ｖ＝６．１６８ｎｍ３，Ｍｒ＝１４２７．４３，Ｚ＝４，Ｄｃ＝１．５４ｇ／ｃｍ３，μ＝１２．４８ｃｍ（－１），Ｆ（０００）＝２８６０，最后偏离因子Ｒ＝０．０６６．     

三羰基环戊二烯基钼负离子与1，3－二卤丙烷的反应

三羰基环戊二烯基钼负离子与１，３－二卤丙烷在一缩二乙二醇二甲醚介质中反应，生成环卡宾配合物ＣｐＭｏＸ（ＣＯ）＿２ＣＯ（ＣＨ＿２）＿２ＣＨ２（Ｘ＝Ｂｒ，Ｉ）．硅桥连双环戊二烯基三羰基钼负离子与１，３－二卤丙烷顺利地进行类似反应，生成相应的硅桥连双［环卡宾钼配合物］──Ｅ［Ｃ＿５Ｈ＿４ＭｏＸ（ＣＯ）＿２］ＣＯ（ＣＨ＿２）＿２ＣＨ＿２］＿２（Ｅ＝Ｍｅ＿２Ｓｉ，Ｍｅ２ＳｉＳｉＭｅ＿２，Ｍｅ２ＳｉＯＳｉＭｅ＿２）．化合物硅氧硅桥联二茂二钼环卡宾配合物１１的晶体结构经Ｘ射线衍射测定，晶体属三斜晶系，Ｐ１空间群，晶体学数据：ａ＝０．８１８８（１）ｎｍ，ｂ＝１．０４５（３）ｎｍ，ｃ＝２．３２５２（４）ｎｍ，α＝９４．１４（２）°，β＝９４．０９（１）°，γ＝１０２．４８（２）°，Ｖ＝１．９３０６ｎｍ￣３，Ｚ＝２，Ｄ＿ｃ＝１．８５４ｇ／ｃｍ￣３。     

［Li（THF）_4］［（t－BuCp）Yb（NPh_2）_3］的合成及晶体结

合成了标题配合物［Ｌｉ（ＴＨＦ）＿４］［ｔ－ＢｕＣｐ）Ｙｂ（ＮＰｈ＿２）＿３］，经元素分析、红外光谱表征，并测定了其晶体结构。配合物属正交晶系，Ｐｂｃａ空间群，晶体学参数ａ＝１．４５１５（５），ｂ＝２．２８３３（５），ｃ＝３．３５５４（６）ｎｍ；Ｖ＝１１．１２０９（５）ｎｍ￣３；Ｄ＿ｃ＝１．３１ｇ·ｃｍ￣＿（－３）；Ｆ（０００）＝４４．２３，Ｚ＝８。最后一致性因子Ｒ＝０．０４７，Ｒ＿ｗ＝０．０４５，平均Ｙｂ－Ｎ键长是０．２２６４（９）ｎｍ。     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates

The processes of thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates were studied. Thermal, chemical and X-ray analyses and infrared spectroscopy were used to determine the mechanisms of decomposition of these complexes. The factor determining the decomposition is the character of the Ag⁺ and Hg ₂ ²⁺ ions, which are easily reduced to free metals. The final reaction product of the compounds of silver is the pure metal; the compounds of mercury are volatilized completely when heated.     

The Solubility of Bis(cyclopentadienyl)samarium(II) and Implications for the Reaction of Samarium Metal with Bis(cyclopentadienyl)mercury(II)

Bis(cyclopentadienyl)samarium(II) has been shown to be insoluble in thf : ether mixtures, hence it cannot be isolated as a soluble product from the reaction of samarium with HgCp₂ in thf : ether.     

Synthesis and Crystal Structure of 4-Chloro-N- （2-（2-nitrophenyl）acetoxy）-N-（m-tolyl）benzamide

The new title compound 4-chloro-N-(2-(2-nitrophenyl)acetoxy)-N-(m-tolyl)benzamide(C22H17ClN2O5, Mr = 424.82) has been synthesized via the reaction of 4-chloro-N-hydroxy-N-(m-tolyl)benzamide with 2-(2-nitrophenyl)acetyl chloride. The structure of the product was confirmed by 1H NMR, 13 C NMR, IR, HRMS(ESI) and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a = 13.0269(10), b = 6.7251(6), c = 23.9313(16) , β = 99.931(6)o, V = 2065.1(3) 3, Z = 4, Dc = 1.366 g/cm3, F(000) = 880, μ = 0.221 mm-1, the final R = 0.0600 and wR = 0.1754 for 1981 observed reflections(I 2σ(I)). X-ray analysis indicates that the chloro-phenyl ring(C(10)~C(15)) and the methyl-substituted benzene ring(C(16)~C(21)) are not coplanar with the nitro-substituted benzene ring(C(1)~C(6)), with the dihedral angle to be 70.78° and 63.72°, respectively. Hydrogen bonds C(2)–H(2)···O(2) and C(7)–H(7B)···O(5) are observed.     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

新型温度敏感性自组装胶束P(NiPAAm-co-DMAA)-co-P(L-Ala)的合成和性能

通过原子转移自由基聚合(ATRP)合成了一种带有活性—NH2基团的温度敏感性亲水型共聚物P(NiPAAm-co-DMAA), 并将其作为引发剂, 合成了P(NiPAAm-co-DMAA)-co-P(L-Ala), 其分子量分布(PDI)在1.3左右. 聚合物通过自组装形成纳米胶束. 透射电镜(TEM)结果表明, 胶束大小200~300 nm, 具有明显的核壳结构. 共聚物的最低临界溶解温度(LCST)为45.5 ℃. 温度低于LCST时, 聚合物溶解形成胶束; 高于LCST时, 胶束解离, 聚合物不溶. 聚合物对温度的响应是快速而可逆的.     

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII)

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII) were obtained in an aqueous solution and in acetonitriie. The rate constants of their decomposition were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 184–185, January, 1995.This work was carried out with financial support from the International Scientific Foundation (Grant REI 000).     

烟酰型辅酶NAD(P)+和NAD(P)H再生的研究进展

大部分氧化还原酶的催化反应需要烟酰型辅酶NAD(P) 和NAD(P)H作为氧化剂或还原剂参与,由于氧化还原酶应用广泛而辅酶价格昂贵,使得辅酶再生逐渐成为研究热点.综述了近年来NAD(P) 和NAD(P)H酶法再生、电化学法及光化学法再生的研究进展,并介绍了各再生技术的应用和开发状况.