若干1，1，2，2-四乙酰基乙烷阴离子(TAE2-)桥联的联吡啶双核铜配合物的合成，结构和磁性

合成了2个以1, 1, 2, 2-四乙酰基乙烷阴离子(TAE^2-)为桥联的双核铜配合物［(bipyCu)(bipyCuH₂O)TAE］(ClO₄)₂·2H₂O(Ⅰ)和(bipyCu)₂TAE(PF₆)₂·3H₂O(Ⅱ)及1个多核铜配合物［CuTAE·2H₂O］_n(Ⅲ)     

若干1,1,2,2-四乙酰基乙烷阴离子(TAE2-)桥联的联吡啶双核铜配合物的合成,结构和磁性

合成了２ 个以１ ,１ ,２ ,２四乙酰基乙烷阴离子（ Ｔ Ａ Ｅ２ － ） 为桥联的双核铜配合物［（ｂｉｐｙ Ｃｕ）（ｂｉｐｙ Ｃｕ Ｈ２ Ｏ） Ｔ Ａ Ｅ］（ Ｃｌ Ｏ４）２ ·２ Ｈ２ Ｏ（ Ⅰ） 和（ｂｉｐｙ Ｃｕ）２ Ｔ Ａ Ｅ（ Ｐ Ｆ６）２ ·３ Ｈ２ Ｏ（ Ⅱ） 及１ 个多核铜配合物［ Ｃｕ Ｔ Ａ Ｅ·２ Ｈ２ Ｏ］ｎ（ Ⅲ） ,并进行了表征。对配合物（ Ⅰ） 进行了 Ｘ射线晶体结构分析,该配合物属于单斜晶系,空间群为 Ｐ２１／ ｎ ,晶胞参数为ａ ＝ ７ ．９２３（１） ．４６５（５） 〓, ｂ ＝ １６ ．０６８（３） 〓, ｃ ＝ ３０ ．１８２（７） 〓, β＝ ９３ ．１８（２）°,晶胞体积 Ｖ＝ ３８３６ ．５（１２） 〓３ , Ｚ＝ ４ , 最终偏离因子 Ｒ１ ＝ ０ ．１１３５ ,ｗ Ｒ２ ＝ ０ ．３１２１ 。磁性质研究表明在这两个双核铜配合物中两个金属铜之间存在弱的反铁磁性相互作用。     

1，1，2，2-四乙酰基乙烷阴离子(TAE2-)桥联的邻菲咯啉双核铜配合物的合成结构和磁性

合成了2个以1, 1, 2, 2-四乙酰基乙烷阴离子(TAE^2-)为桥联的双核铜配合物［(bipyCu)(bipyCuH₂O)TAE］(ClO₄)₂·2H₂O(Ⅰ)和(bipyCu)₂TAE(PF₆)₂·3H₂O(Ⅱ)及1个多核铜配合物［CuTAE·2H₂O］_n(Ⅲ)     

1,1,2,2-四乙酰基乙烷阴离子(TAE2-)桥联的邻菲咯啉双核铜配合物的合成结构和磁性

合成了两个以1,1,2,2-四乙酰基乙烷阴离子(TAE2-)为桥联的双核铜配合物(Cuphen)2TAE(ClO4)2.4H2O(Ⅰ)和[(phenCu)(phenCuCl)TAE](ClO4).4H2O(Ⅱ),并进行表征.对配合物(Ⅱ)进行了X-射线晶体结构分析,该配合物属于单斜晶系,空间群为C2/c(No.15),晶胞参数为a=25.465(5),b=13.064(3),c=12.125(2),β=110.72(3)°,晶胞体积V=3773(2)3, Z=4,最终偏离因子R=0.070, Rw=0.074.磁性质研究表明在这两个双核铜配合物中两个金属铜之间存在弱的反铁磁性相互作用.     

氯冉酸阴离子桥联双核铜(II)配合物的合成和磁性

本文合成了五种以氯冉酸二价阴离子为桥联配体的Cu(II)单核([CuLCA].H~2O)和双核([Cu~2L~2CA](ClO~4)~2配合物:[Ca(phen)CA].H~2O(1),[Cu~2(phen)~2CA](ClO~4)~2(2),[Cu(NO~2-phen)CA].H~2O(3),[Cu~2(NO~2-phen)~2CA](ClO~4)~2(4)和[Cu~2(bpy)~2CA](ClO~4)~2(5)。经元素分析、红外、固体紫外、顺磁共振、磁化率及变温磁化率的测定对上述各配合物进行了表征。配合物1,3可能是通过水分子中的氢键将两个[CuLCA]单元联接而缔合的假双聚体。配合物2,4,5则由阳[Cu~2L~2CA]^2^+阳离子和弱配位的ClO~4^-阴离子所组成。双核配合物中Cu(II)离子的几何构型可能为畸变的四方锥。所有五种配合物均难溶于水及常见有机溶剂。上述配合物的室温ESR谱呈现ΔM~s=2的从单重态到三重态的半场跃迁。配合物2,5的变温磁化率(4-300K)已测得,利用Heisenberg模型确定交换参数J值为-29.2和-25.7cm^-^1。表明在此类桥联配合物中,两核间存在着反铁磁性交换耦合作用。     

氯冉酸阴离子桥联双核铜(II)配合物的合成和磁性

本文合成了五种以氯冉酸二价阴离子为桥联配体的Cu(II)单核([CuLCA].H~2O)和双核([Cu~2L~2CA](ClO~4)~2配合物:[Ca(phen)CA].H~2O(1),[Cu~2(phen)~2CA](ClO~4)~2(2),[Cu(NO~2-phen)CA].H~2O(3),[Cu~2(NO~2-phen)~2CA](ClO~4)~2(4)和[Cu~2(bpy)~2CA](ClO~4)~2(5)。经元素分析、红外、固体紫外、顺磁共振、磁化率及变温磁化率的测定对上述各配合物进行了表征。配合物1,3可能是通过水分子中的氢键将两个[CuLCA]单元联接而缔合的假双聚体。配合物2,4,5则由阳[Cu~2L~2CA]^2^+阳离子和弱配位的ClO~4^-阴离子所组成。双核配合物中Cu(II)离子的几何构型可能为畸变的四方锥。所有五种配合物均难溶于水及常见有机溶剂。上述配合物的室温ESR谱呈现ΔM~s=2的从单重态到三重态的半场跃迁。配合物2,5的变温磁化率(4-300K)已测得,利用Heisenberg模型确定交换参数J值为-29.2和-25.7cm^-^1。表明在此类桥联配合物中,两核间存在着反铁磁性交换耦合作用。     

碘冉酸阴离子桥联双核铜（Ⅱ）配合物的合成与磁性

碘冉酸阴离子桥联双核铜（Ⅱ）配合物的合成与磁性孟祥军寇会忠邹国彰廖代正姜宗慧＊王耕霖（南开大学化学系天津３０００７１）关键词碘冉酸，Ｃｕ（Ⅱ），双核配合物，合成，磁性１９９６－０８－２０收稿，１９９６－１１－１８修回国家自然科学基金资助项目随着生物无...     

叠氮阴离子μ-1,1桥联双核Co(Ⅱ)配合物的合成及其晶体结构和磁性

用水热法合成了以邻菲啰啉(phen)为辅助配体叠氮桥联Co2+配位聚合物:[Co2(μ1,1-N3)2(phen)2(N3)2]。用IR和元素分析进行了表征,用单晶XRD测定晶体结构,属于三斜晶系,P1空间群,a=0.69272(14)nm,b=1.0318(2)nm,c=1.0381(2)nm,α=6.447(3)°,β=71.02(3)°,γ=85.79(3)°,Z=1,V=0.6312(2)nm3,D=1.701 mg/mm3,F(000)=326。确定N3-为μ-1,1桥联配位。测定了配合物固体的变温磁化率,证明配合物为亚铁磁性物质,其临界温度为15 K。     

桥联双核铜席夫碱配合物的合成和晶体结构

利用1-苯基-3-甲基-5-吡唑啉酮和水杨酰胺制备了PMP缩水杨酰胺席夫碱及其铜(Ⅱ ) 配合物,根据红外和紫外光谱数据表征了它的结构.利用X射线衍射方法研究了配合物的晶体结构,结果表明配合物为桥联双核铜结构,铜原子为五配位的四方锥构型,每个铜原子与一个配体中吡唑啉酮上的氧原子、席夫碱上的N原子、水杨酰的酚氧原子和溶剂DMF中的氧原子配位,而相邻配体中水杨酰的酚氧原子也参加配位并将两个铜原子连接起来形成桥联双核铜配合物,两个Cu(Ⅱ )原子间的距离为0.3268 nm.芳环堆积作用和分子内及分子间氢键的存在增强了配合物分子的稳定性.     

邻苯二甲酸单甲酯桥联双核铜(Ⅱ)配合物磁性的理论研究

采用对称性破损态方法结合密度泛函理论,选用典型的强反铁磁双核配合物作为研究对象,通过与实验数据相比较,探讨了不同密度泛函方法与基组对计算铜配合物[Cu2(mMP)4(H2O)2]·H2O交换耦合常数的准确度.结果表明,4种混合密度泛函DFT(B3LYP,B3P86,B3PW91和PBE0)的计算结果都能和实验所观察到的值-324cm-1符号一致,但B3PW91方法得到的结果和实验结果吻合程度最好,同时采用方法B3PW91方法计算所得的交换耦合常数Jab对基组的依赖性较大.研究表明,2个Cu(Ⅱ)离子之间的反铁磁相互作用主要源于单占据分子轨道SOMOs大的能量劈裂和桥联配体O-C-O轨道的重叠.     

SYNTHESIS AND CRYSTAL STRUCTURE OF OXAMIDATO-BRIDGED BINUCLEAR COPPER(II) COMPLEXES

Abstract

The compounds [Cu(oxpn)] (1), [(bpy)(H₂O)Cu(μ-cis-oxpn)Cu(H₂O)] · 2NO₃ · 2H₂O (2) and [(Him)(NO₃)Cu(μ-trans-oxpn)Cu(Him)(NO₃)] (3), where oxpn is the dianion of N,N′-bis(3-aminopropyl)oxamide, bpy is bipyridine and Him is imidazole, were prepared and characterized by elemental analysis and IR spectra. Complex (2) was also studied by thermochemical analysis and its structure determined by X-ray crystallography. The structure of complex (2) consists of binuclear copper(II) molecules in which the copper(II) atoms are bridged by an oxamidato group in the cis conformation resulting a copper-copper distance of 5.21 Å. Both copper(II) ions are in square-pyramidal surroundings with almost coplanar basal planes and a water molecule occupying the apical positions. The N atoms of the oxamidato moiety are trigonal. Two lattice water molecules together with the two coordinated ones hydrogen bond with nitrate ions.     

2，6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜（Ⅱ）配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：〔Ｃｕ２（Ｌ）（μ─Ｃｌ）Ｃｌ２〕，配体Ｌ为２，６─二甲酰─４─甲基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）．配合物具有相同的组成和配位构型．变温磁化率（４－３００Ｋ）测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ（－１）（Ｌ１）和－５７．６ｃｍ（－１）（Ｌ２）．     

2, 6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜(Ⅱ)配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：［Ｃｕ２（Ｌ）（μ－Ｃｌ）Ｃｌ２］，配体Ｌ为２，６－二甲酰－４－基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）。配合物具有相同的组成和配位构型。变温磁化率测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ＾－１（Ｌ１）和－５７．６ｃｍ＾－１（Ｌ２）。     

双-(磷酸二甲酯)合铜的红外光谱与晶体结构

合成了单元化学式为-Cu[(CH_3O)_2PO_2]_2-的铜(Ⅱ)与磷酸二甲酯的配位聚合物。测定了4000—100 cm~(-1)谱区内的红外光谱, 讨论了某些谱带的归属, 解释了配位化合物形成后的光谱变化。由单晶X-射线衍射法确定此配合物的晶体属单斜晶系,空间群为P2_1/c, 晶胞参数a=1.0704(4), b=0.5093(2), c=1.9737(6) nm; β=96.23(3)°; V=1.0696(6) nm~3; Z=4. M=313.5, F(000)=636e, D_c=1.943 g·cm~(-3)。铜与五个配体中的五个非酯氧配位成四角锥体, 相邻两铜原子以对称的“O—P—O”桥和不对你的“O—P—O”桥相连, 形成一维链状配位聚合物。     

SYNTHESIS,CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF A MANGANESE(III) COMPLEX WITH SALICYLATE AND IMIDAZOLE LIGANDS

Abstract

A new manganese(III) complex [HimH][Mn(sal)₂(imH)₂]CH₃OH (sal = salicylate, C₇H₄O₃ ^2-; imH = imidazole, C₃H₄N₂; [HimH]⁺ = imidazole cation (C₃H₅N₂) has been prepared and characterized by X-ray analysis and magnetic measurements. The compound crystallizes in the monoclinic space group P2 ₁ with a = 9.931(2), b = 10.237(1), c = 12.926(7) Å, β = 102.740° and Z = 2. The structure has been refined to R = 0.030 and R_w = 0.031. The Mn(III) ion has elongated octahedral coordination with mutually trans imidazoles occupying axial sites. The equatorial plane is defined by four O atoms of two salicylates. Each [HimH]⁺ cation (imidazolium) is associated with two complex anions through hydrogen bonds as an imidazolium bridge. The variable temperature magnetic susceptibility for the complex in the temperature range 77-300 K has been interpreted in terms of a single-ion zero-field splitting model with a molecular field term correction. The values obtained for D, g. and zj' are -6.93 cm^?1, 2.00 and -0.90 cm^?1.     

CRYSTAL STRUCTURE AND X-RAY CRYSTALLOGRAPHIC ANALYSIS OF THE BINUCLEAR CLUSTER THIOCYANATE COMPLEX OF NIOBIUM(IV)

Journal of Structural Chemistry - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound...     

CRYSTAL STRUCTURE,SPECTRAL AND MAGNETIC BEHAVIOR OF COPPER(II)(5-CHLOROSALICYLATO)2 (AQUA)2

Abstract

The synthesis and characterization of Cu(5-Clsal)₂(H₂O)₂ (5-Clsal = 5-chlorosalicylate) are reported. Characterization of the compound was based on elemental analysis, electronic and EPR spectra, and magnetic susceptibility measurement over a temperature range 93–239 K.

An X-ray analysis of Cu(5-Clsal)₂(H₂O)₂ was carried out, showing a polymeric chain of copper(II) atoms bridged by pairs of water molecules with Cu-O(bridge) bond lengths of 1.970(2) and 2.718(2)Å. The coordination sphere about each copper(II) atom is completed (on the X-axis) by a trans-pair of unidentate 5-chlorosalicylate anions. The bridging oxygen atoms arrange a planar Cu₂O₂ rhombus. The relationship between degree of distortion and g-values from EPR spectra is also discussed.     

PREPARATION AND CRYSTAL STRUCTURE OF THE HOST-GUEST TYPE COMPLEX OF TRIS(BIPYRIDINE)NICKEL(II)-TETRAKIS(CYANO) NICKELLATE (II))-HEXAHYDRATE-HEMI (BIPYRIDINE)

Abstract

The title complex is built up of [Ni(bpy)₃]²⁺ cations, [Ni(CN)₄]^2? anions and non-coordinated bpy and water molecules. The water molecules along with one of the two crystallographically independent tetracyanonickellate anions form layers, in which H-bonds (HB's) of the types O-H ‥ O and O-H ‥ N are important. The remaining tetracyanonickellate anions bound by H-bonds to water molecules in the layers are placed approximately perpendicular to the layers making interconnection between them. So by HBs a 3D network is formed (hydrophilic host part of the structure). The cations and non-coordinated bpy molecules (hydrophobic guest part of the structure) are placed in cavities formed by HBs. The Ni-N distances in the cation are within the range 2.078(3)-2.100(3) Å and the Ni-C distances in the anion are within the range 1.854(5)-1.873(4) Å.