[Cu(H2O)(phen)2](CIO4)2的晶体结构

标题化合物晶体属三斜晶系;空间群为P₁;晶胞参数:a=8.182(2)Å,b=10.389(2)Å,c=16.261(5)Å,α=99.38(2)°,β=89.97(2)°,γ=113.18(2)°;Z=2,两个phen上的四个N原子和一个配位水中的O原子围绕中心体Cu原子形成一个畸变的三角双锥构型,配位水与阴离子ClO₄^-中的O原子形成氢键。     

{[Sm_2(Gly)_6(H_2O)_4](ClO_4)_6(H_2O)_5}_n的合成和晶体结构

本文合成了标题配合物,对其红外光谱进行了研究.测定了配合物的晶体结构,结果表明,晶体属三斜晶系,P1空间群,单胞参数:α=11.549(2)(?),b=14.122(3)(?),c=15.654(?),α=97.01(2)°,β=102.70(2)°,γ=105.43(2)°,V=2355.94(0.87)(?)~3,Z=2.晶体结构是采用Patterson法和差值Fourier合成解出.经全矩阵最小二乘法修正,最后偏差因子R=0.0337,R_w=0.0364.晶体中甘氨酸与Sm原子的结合方式有三种:第一种甘氨酸的羧基离子以螯合桥式与Sm原子配位;第二种甘氨酸以羧基桥式与同一单元的两个Sm原子配位;第三种甘氨酸以酸基桥式连结两个相邻单元中的相邻Sm原子而形成一维无限长链结构.此外,每个Sm原子还与两个水分子成键,其配位数为9.     

Roussin红盐衍生物[Fe_2(μ_2-SC_6H_4F)_2(NO)_4]的晶体与分子结构

Roussin黑盐与重氮盐反应,可以得到络合物[Fe-2S_2(C_6H_4F)_2(NO)_4]。它是一种暗红色的晶体,属于三斜晶系,空间群P_~-,晶胞参数a=10.217 4),b=10.143(1),c=8.955(1),α=105.68(4)°,β=99.91(2)°,Υ=83.44(2)°,Z=2。应用X射线衍射方法测定晶体结构。由重原子法解出结构,并经全矩阵最小二乘法修正,R=0.029。单胞中的两个分子以对称心相连系。Fe原子为四面体配位,两个-SR基团上的S原子以桥键与两个Fe原子构成Fe_2S_2的菱形平面,四个-NO基则分别与两个Fe原子配位。     

Co(μ_2-bpy)V_2O_6(bpy=4,4''''-联吡啶)的水热合成和晶体结构

采用CoCl2·6H2O、4,4'-联吡啶和NH4VO3,以H2O作溶剂(摩尔比1∶2∶2∶1950)在170℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6(bpy=4,4'-联吡啶),经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pī,晶胞常数a=0.81599(7)nm,b=0.85826(7)nm,c=1.02031(8)nm,α=87.111(2)°,β=75.305(2)°,γ=74.784(2)°,Z=2.Co(μ2-bpy)V2O6是无机的双金属氧化物层,犤Co2V4O12犦n通过有机的桥式配体μ2-bpy以N-Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5nm×0.7nm.漫反射光谱研究表明,此晶体具有约2.0eV的光学能隙,属于半导体,在420℃以下是热稳定的.     

Er(PMAP)_3·2H_2O的合成及其晶体结构和分子结构

Er(PMAP)_9·2H_2O(PMAP=1-苯基-3-甲基-4-乙酰吡咯啉酮-5)属单斜晶系。空间群为P2_1/c,晶胞参数α=17,582(4),b=12.346(2),c=18.236(3),β=102.8(2)°,Z=4,R=0.06298。     

[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)、2,2-联吡啶(C_(10)H_8N_2,简写bipy)与Eu(NO_3)_3·4H_2O反应,首次培养出黄色单晶[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O.该晶体属三斜晶系,空间群为P-1,晶胞参数a=0.93392(16)nm,b=1.3100(2)nm,c=1.3895(2)nm,α=97.205(3)°,β=105.411(2)°,γ=106.364(2)°,V=15.35(2)nm~3,Z=2,μ=2.118mm~(-1),Dc=1.686Mg/m~3,F(000)=786,R=0.0116,wR=0.0507,GOF=0.995.晶体测试结果表明,该单晶结构为铕的9配位配合物,两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位;每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu~(3+)配位,形成两个共边的稳定五元环,另三个配位原子则分别来自三个水分子中的氧原子,该配合物在空间呈扭曲的单帽四方反棱柱,而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子,这些游离分子与配位分子之间存在大量分子内和分子间氢键,整个分子在空间呈三维网状结构.发光性能测试表明该配合物具有很好的荧光性质.     

氨三乙酸桥连的3d-4f金属异核配合物:{[GdCu(NTA)(H_2O)_6Cl]ClO_4·H_2O}_n的合成和晶体结构

合成了金属异核配合物{[GdCu (NTA ) (H2 O ) 6 Cl]ClO4·H2 O}n,通过单晶衍射测定其结构。配合物的晶体属三斜晶系 ,空间群P 1 ,a =0 84 830 ( 1 0 )nm ,b =0 9642 ( 2 )nm ,c =1 2 838( 2 )nm ,α =1 1 1 1 70( 1 0 )° ,β =93 52 0 ( 1 0 )°,γ =1 0 0 890 ( 1 0 )°,V =0 9530 ( 3)nm3,Z =2 ,Dc=2 335g·cm- 3。配合物的晶体呈现锯齿状一维链状结构。铜离子是五配位 ,配位多面体是一个扭曲四棱锥。每个NTA通过其氮原子和 3个羧基的 3个氧原子与铜离子螯合 ,形成 3个五元环 ,氯离子也与铜离子配位。ClO- 4作为平衡离子位于链间。     

[La(Phen)2(NO3)2(H2O)2]ClO4·2Phen·H2O的合成与晶体结构

合成了[La(Phen)2(NO3)2(H2O)2]ClO4·2Phen·H2O(1,化学式为C48H38ClN10O13La,Mr=1137.24,Phen=邻菲咯啉),经X-射线单晶衍射测定其晶体结构属于三斜晶系,Pī空间群,a=11.250(4),b=13.364(4),c=16.327(5)(。A),α=103.042(6),β=90.327(6),γ=99.567(6)°,V =2355.8(12)(。A)3,Z = 2,Dc =1.603g·cm-3,F(000)=1148,μ=1.042mm-1,R=0.0569,wR= 0.1064.1由 [La(Phen)2(NO3)2(H2O)2]+ 阳离子,ClO-4阴离子,两个共结晶的Phen分子和1个H2O分子构成.内界的中心金属La(III)离子为十配位的变形的双帽四方反棱柱体,其配位环境分别被6个来自两个双齿配位硝基和两个H2O分子的氧原子和4个来自两个Phen配体的氮原子所包围,形成单核+1价阳离子,外界有1个水分子,1个ClO-4阴离子和两个Phen分子构成.整个分子通过分子间氢键形成3D网络结构.     

[Ni(C_5H_5N)_2(C_7·H_6O_2N)_2]H_2O三元配合物的合成及晶体结构

合成了标题化合物。该化合物的分子式[Ni(C5H5N)2(C7H6O2N)2]H2O(C24H24N4NiO3),分子量475.18,采用单色的MoKα (λ = 0.71073 )射线测定,共收集7408个数据,其中独立衍射点2567个(Rint = 0.0272),I > 2s(I)可观测点数1926个,结果表明该化合物属单斜晶系, 空间群C2/c其晶胞参数为: a = 14.466(2),b = 12.193(2),c = 14.072(2) ;β = 116.229(2)°,V = 2226.6(5) 3,Z = 4,Dc = 1.418 g/cm3 ,μ = 0.905 mm-1,F(000) = 992. 2个水杨醛亚胺各提供2个配位原子参与配位,2个吡啶各提供1个配位原子参与配位,该配合物是六配位的八面体构型,同时讨论了该体系中不同配位原子的配位能力的差异。     

[Cu(Phen)_3][DTB]·6H_2O的合成与晶体结构

利用螯合配体1,10-邻菲咯啉(Phen)与2,2′-二硫代二苯甲酸(H2DTB)的钠盐及氢氧化铜反应合成了一种新型配合物[Cu(Phen)3][DTB].6H2O,通过元素分析、红外光谱和X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群P2(1)/c,晶胞参数:a=1.822(2)nm,b=3.053(4)nm,c=2.016(3)nm,α=90°,β=106.28(4)°,γ=90°,Z=8,V=10.762(25)nm3,Dc=1.255 g/cm3,Mr=1016.57.该配合物晶体结构由配阳离子[Cu(Phen)3]2+和未配位的反荷阴离子[DTB]2-和晶格水分子组成.每个Cu(Ⅱ)原子与来自三个Phen的6个N原子配位,形成畸变的八面体结构单元.     

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).     

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.     

(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).     

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.

     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

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.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

草酸根桥联的不对称双核铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成与磁性

本文合成了一组新的不对称的双核配合物,[Cu_2(C_2O_4)_2terp]和〔Cu Zn(C_2O_4)_2terp〕(图1),terp表示联三吡啶。配合物〔Cu_2(C_2O_4)2terp〕的变温磁化率已测,其数值已用最小二乘法与Bleaney-Bowers方程拟合,求得交换积分J=-47.20cm~(-1)。文中还用Kahn理论解释了这种较弱的反铁磁自旋交换作用。     

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.