Na[Co(OX)_2(N,N’-Me_2en)]的合成、异构体分离、空间构型推定和性质研究

合成了具有三个手性原子的二草酸根、N,N＇-二甲基乙二胺合钴(Ⅲ)酸钠配合物.用离子交换法分离了该配合物三对可能的对映体:△(SS)(?)(RR)、△(SR)(?)(RS)和△(RR)(?)(SS)对映体,用质子核磁共振法推定了异构体的空间构型,用高效液相色谱法测定了三对对映体的平衡生成率,其相对比值(34.0℃)为:△(SS)(?)(RR):△(SR)(?)(RS):△(RR)(?)(SS)=58:33:9.各对映体d-d跃迁最大吸收峰波数次序为:△(SS)(?)(RR)>△(SR)(?)(RS)>△(RR)(?)(SS).     

[Tb(CH3COO)3(H2O)2]2的合成及其结构测定

2-羟基吡啶、希土高氯酸盐和乙酸钴在乙腈中反应,制备了九配位化合物[Tb(CH₃COO)₃·2H₂O]₂该晶体为三斜晶系,P1空间群,其晶胞参数为a=8.870(4)Å,b=9.247(1)Å,c=10.586(1)Å,α=65.13(1)°,β=64.43(2)°,γ=62.16(4)°,V=665.97ų,Z=1,F(000)=394。测定了配合物的红外光谱。讨论了它的生成机制。     

乙二醇二甲醚三苯基氧化膦三氯合铬Cr[(CH3OCH2CH2OCH3)(OPPh3)Cl3]的合成和晶体结构

标题配合物由Cr(CO)₆和PPh₃在50ml乙二醇二甲醚中回流5小时后过滤,在滤液中加S₂Cl₂,静置后得配合物单晶。晶体属单斜晶系,空间群为P2₁,单胞参数a=9.062(3)Å,b=11.088(3)Å,c=12.153(3)Å,β=97.93(1)°,V=1209.4(1.8)ų,Z=2。 晶体结构是采用Patterson法和差Fourier合成解出。经全矩阵最小2乘法修正,最后偏离因子R=0.046,R_ω=0.054,结构中Cr各与三个氧和三个氯原子键联,Cr-O(CH₃OCH₂CH₂OCH₃)平均距离为2.091Å,Cr-O(OPPh₃)距离为2.000Å,Cr-Cl(平均)距离为2.274Å。它们形成了八面体配位构型。     

混合金属配合物MoS4Cu2(NC5H5)4的合成、晶体结构和成键特点

混合金属配合物MoS₄Cu₂(NC₅H₅)₄(NC₅H₅=吡啶)的晶体属于三斜晶系P1空间群,晶胞参数:a=9.465(50),b=9.463(4),c=14.053(3)Å,α=95.16(3),β=84.89(3),γ=95.91(4)°,Z=2,V=1243(2)ų;Mr=667.7,D_c=1.784g·cm^-3.R因子为0.039,加权R_w因子为0.045.该配合物簇骼具有D_2d对称性,Mo-Cu间距分别为2.638Å,2.663Å.端配体吡啶与金属原子Cu间的d-π^*反馈在一定程度上增强了Mo—Cu间的相互作用.     

钌(Ⅱ)配合物[Ru(dpq)2L]4+的合成、晶体结构及与G-四链体DNA的相互作用

以cis-[Ru(dpq)₂Cl₂]·2H₂O(dpq=二吡啶[3,2-d:2',3'-f]二氮萘)为原料与5,5'-二(1-(三乙胺)甲基)-2,2'-联吡啶阳离子(L)合成钌(Ⅱ)配合物[Ru(dpq)₂L](PF₆)₄,并研究了该配合物与G-四链体DNA的作用:FRET实验表明,配合物对人端粒DNAh-telo具有选择性,其作用能力要强于同癌基因启动子区域的四链DNA,如c-myc和bcl2;CD光谱表明,在Na⁺和K⁺都不存在的情况下,配合物能诱导h-telo形成平行结构;此外,紫外和发射光谱都显示,配合物在K⁺溶液中与h-telo的作用力要大于在Na⁺溶液中的。     

镍(Ⅱ)、镉(Ⅱ)与去甲基斑蝥酸钠和咪唑配合物的结构、与DNA/BSA的作用及抗增殖活性

以2种配体去甲基斑蝥酸钠(Na₂DCA=7-氧杂二环[2.2.1]庚烷-2,3-二甲酸钠)和咪唑(IM),分别与镍(Ⅱ)和镉(Ⅱ)的醋酸盐通过溶液法合成了2种配合物[Ni(IM)(DCA)(H₂O)₂]·2H₂O(1),[Cd₂(IM)₄(DCA)₂]·2H₂O(2)。应用元素分析、热重分析、红外光谱及X-射线单晶衍射法对配合物的组成和结构进行了表征。配合物1与2的中心离子分别与咪唑的亚胺氮原子、去甲基斑蝥酸根的羧基氧原子和醚键氧原子配位,配位数均为6,分别为单核(1)和双核(2)配合物。通过紫外光谱法、荧光光谱法和粘度法研究了配合物与DNA的相互作用。结果表明,配合物能通过部分插入模式与DNA发生较强的结合作用(K_b:5.51×10³(1)、1.01×10³(2)L·mol^-1)。同时,利用荧光光谱法研究了配合物与牛血清白蛋白(BSA)的相互作用。配合物能与BSA发生强烈的相互作用(K_AM:1.91×10⁵(1)和6.17×10⁵(2)L·mol^-1),结合位点数均为1。测试了配合物对人肝癌细胞(SMMC₇₇₂₁)和人乳腺癌(MCF-7)的体外抗增殖活性。结果显示,配合物对不同癌细胞具有选择性抑制作用。镍配合物(1)对SMMC₇₇₂₁的抗癌活性较去甲基斑蝥酸钠有明显提高。     

单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu2(OH)(ClO4)(C16H38N6)](ClO4)2·CHCl3的合成和结构

本文合成了单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu₂(OH)(ClO₄)(C₁₆H₃₈N₆)](ClO₄)₂·CHCl₃,并测定与讨论了它的晶体结构.晶体属于正交晶系,空间群为D₂⁴-P2₁2₁2₁,晶胞参数:a=12.749(4)Å,b=14.361(3)Å,c=18.064(3)Å,V=3307.3(13)ų,Z=4.分子结构中单羟基桥连两个二价铜离子,Cu-O平均键长为1.935(6)Å,Cu-OH-Cu键角为135.2(2)°;铜原子的几何构型为畸变四方锥,配体的底面为穴醚的二乙三胺亚基的三个氮原子和一个羟基桥氧原子;顶点位置为高氯酸根的氧原子,因为该原子同时配位于另一个铜原子,所以分子的双铜中心存在第二个氧桥,即较弱的高氯酸根桥;Cu-O(ClO₃)距离分别为3.005(9)Å和2.806(8)Å.     

μ3-O-{[μ-(n-Bu)2Sn(μ-FcCO2)(n-Bu)2Sn]FcCO2}二聚物的晶体结构和分子结构

标题配合物Mr=933.84,属单斜晶系,空间群P2₁/n,晶胞参数a=15.244(4)Å,b=20.895(7)Å,c=12.375(4)Å,β=97.39(3)°,Z=4,V=3909(2)ų,Dc=1.5879·cm^-3,F(000)=1872,最终偏差因子R=0.0684.该配合物分子呈中心对称,是具有Sn₂O₂中心内环的二聚体,Sn₂     

氧桥桥连四核M4[2×2]格子状结构锌(Ⅱ)配合物的自组装、晶体结构及荧光性质

以席夫碱碳腙类配体H₂L自组装合成了一个新的M₄[2×2]四方格子状结构锌(Ⅱ)配合物[Zn₄(HL)₄](ClO₄)₄·2MeCN·2MeOH(H₂L=1,5-bis(1-(pyridine-2-yl)ethylidene)carbonhydrazide),并对其进行了元素分析、红外光谱、紫外可见光谱和X-射线单晶衍射法表征。单晶结构分析结果表明配合物中,Zn(Ⅱ)离子具有N₄O₂型扭曲的八面体配位构型,4个配体分别失去1个质子后以醇式与金属离子配位,由4个酚氧原子桥连4个Zn(Ⅱ)离子形成[2×2]格子状结构四核配合物。固态荧光测试表明配合物在530 nm附近有强的荧光发射峰。     

氧桥桥连四核M4[2×2]格子状结构锌(Ⅱ)配合物的自组装、晶体结构及荧光性质

以席夫碱碳腙类配体H₂L自组装合成了一个新的M₄[2×2]四方格子状结构锌(Ⅱ)配合物[Zn₄(HL)₄](ClO₄)₄·2MeCN·2MeOH(H₂L=1,5-bis(1-(pyridine-2-yl)ethylidene)carbonhydrazi-de),并对其进行了元素分析、红外光谱、紫外可见光谱和X-射线单晶衍射法表征。单晶结构分析结果表明配合物中,Zn(Ⅱ)离子具有N₄O₂型扭曲的八面体配位构型,4个配体分别失去1个质子后以醇式与金属离子配位,由4个酚氧原子桥连4个Zn(Ⅱ)离子形成[2×2]格子状结构四核配合物。固态荧光测试表明配合物在530nm附近有强的荧光发射峰。     

三维超分子[Ni(hmt)2(SCN)2(H2O)2][Ni(SCN)2(H2O)4](H2O)2的自组装,晶体结构及磁性质(hmt=六次甲基四胺)

Compound [Ni(hmt)₂(SCN)₂(H₂O)₂][Ni(SCN)₂(H₂O)₄](H₂O)₂ (hmt=hexamethylenetetramine) was pre-pared and structurally characterized by means of X-ray single crystal diffraction. The two neutral units [Ni(hmt)₂(SCN)₂(H₂O)₂] and [Ni(SCN)₂(H₂O)₄] are joined together through hydrogen bonds N…H-O, O…H-O and S…H-O. In the solid state, the compound has three-dimensional network structure. The determination of its variable-temperature magnetic susceptibilities (5～300K) shows that the magnetic behavior obeys the Curie-Weiss law over the whole temperature ranges.     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

双核钼铁硫簇合物[Fe(2, 2''-联吡啶3)][(S2MoS2FeCl2]的合成与晶体结构

双核Mo-Fe-S原子簇配合物[Fe(2,2′-bpy)₃][S₂MoS₂FeCl₂],是(Et₄N)₂MoS₄、FeCl₂和2,2′-联吡啶在乙腈中反应得到的结晶化合物.晶体属单斜晶系,空间群P2₁/c;a=9.328(3),b=26.788(2),c=13.764(3)Å;β=95.38(3)°;V=3424.2(11)ų;Z=4;D_c=1.698g/cm³;F(000)=1752.晶体结构用直按法解出;经全矩阵最小二乘法修正,最后R=0.068,R_ω=0.071(3933个I>3(σ)(I)的独立衍射).在晶体结构中配位阴离子[S₂MoS₂FeCl₂]^2-是排布在阳离子[Fe(2,2′-bpy)₃]²⁺所形成的空腔中.它是以非统计分布的形式存在,从而较准确地测定了各项键参数.Mo…Fe距离为2.773(2)Å,Mo-S_b和Fe-S_b有大致相等的键长.     

混合价四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]•H2O的合成、晶体结构及性质研究

在乙腈溶液中, 由混合价三核锰配合物[Mn₃O(ClCH₂COO)₆(py)₂]•(H₂O) (py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn₃^IIIMn^II)四核锰配合物[Mn₄O₂(ClCH₂COO)₇(bipy)₂]•H₂O. 采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构. 标题化合物晶体属于三斜晶系, 空间群P-1, 晶胞参数: a＝0.89854(13) nm, b＝1.4027(2) nm, c＝1.9037(3) nm, α＝93.518(3)°, β＝96.736(3)°, γ＝94.875(3)°, V＝2.3680(6) nm³, Z＝2, D_c＝1.734 g/cm³, F(000)＝1238, GOF＝1.036, R₁＝0.0592, wR₂＝0.1162 [I＞2σ(I)]. 在标题化合物中, 配位结构单元中心为一蝶型[Mn₄(μ₃-O)₂]^7＋多核簇, 含有2个Mn₃(μ₃-O)单元, 具有近似C₂对称轴. 4个Mn离子均为六配位, 外围配体为7个氯乙酸根和2个2,2′-联吡啶, 处于变形的八面体环境. 变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用, 但在低温下的磁相互作用较为复杂.     

(NO2Ql)2[Ni(mnt)2]的合成和晶体结构((NO2Ql)+=1-(4-nitrobenzyl)-quilorinium;mnt2-=maleonitriledithiolate)

合成了离子对配合物(NO2Q1)2[Ni(mnt)2],并用元素分析和红外光谱进行了表征.单晶结构分析结果表明三斜晶系,空间群p-1.晶胞参数a=8.2240(16)A,6=10.777(2)A,c=12.137(2)A,α=72.58(3).,β=72.82(3)°,γ=68.78(3)°,V=935.4(3)A3,Z=1.(NO2Ql)+和[Ni(mnt)2]2-分别形成了完全分立的柱状堆积结构.在阴离子堆积柱内,Ni(Ⅱ)离子形成了一维均匀链.阳离子间,比邻的芳环间存在弱的π…π作用.     

Synthesis and crystal structure of Ir(C2H4)2(C5H7O2)

We report a new synthesis and characterization of Ir(C₂H₄)₂(C₅H₇O₂) [(acetylacetonato)-bis(η²-ethene)iridium(I)], prepared from (NH₄)₃IrCl₆ · H₂O in a yield of about 45%. The compound has been characterized by X-ray diffraction crystallography, infrared, Raman, and NMR spectroscopies and calculations at the level of density functional theory. Ir(C₂H₄)₂(C₅H₇O₂) is isostructural with Rh(C₂H₄)₂(C₅H₇O₂), but there is a substantial difference in the ethylene binding energies, with Ir-ethylene having a stronger interaction than Rh-ethylene; two ethylenes are bound to Ir with a binding energy of 94 kcal/mol and to Rh with a binding energy of 70 kcal/mol.     

Synthesis, characterization, and substituent effects of mononuclear ruthenium complexes [RuCl(CO)(PMe3)3(CHCH-C6H4-R-p)] (R = H, CH3, OCH3, NO2, NH2, NMe2)

A series of mononuclear ruthenium complexes [RuCl(CO)(PMe₃)₃(CHCH-C₆H₄-R-p)] (R = H (2a), CH₃ (2b), OCH₃ (2c), NO₂ (2d), NH₂ (2e), NMe₂ (2f)) has been prepared. The respective products have been characterized by elemental analyses, NMR spectrometry, and UV-Vis spectrophotometry. The structures of complexes 2c and 2d have been established by X-ray crystallography. Electrochemical studies have revealed that electron-releasing substituents facilitate monometallic ruthenium complex oxidation, and the substituent parameter values (σ) show a strong linear correlation with the anodic half-wave or oxidation peak potentials of the complexes.     

Synthesis and molecular structure of [Mg(CH2SiMe3)(μ-OCH2SiMe3)]4

Crystalline [Mg(CH₂SiMe₃)(μ³-OCH₂SiMe₃)]₄ has been identified as the product of oxidation of ClMgCH₂SiMe₃ with traces of O₂. Its formation requires the formation of Mg(CH₂SiMe₃)₂ via the Schlenk equilibrium. The compound is a rare example of a structurally characterized magnesium alkyl alkoxide with Mg₄O₄ cubane structure.     

Crystal structure of a novel Hg(II) complex, [Hg(tri-2-furylphosphine)2(tri-2-furylphosphinoxide)3] [ClO4]2

The Hg(II) complex [Hg(TFP)₂(OTFP)₃][ClO₄]₂ with TFP=tri-2-furyl-phosphine and OTFP=tri-2-furylphosphinoxide has been prepared and characterised. It crystallises in the hexagonal P6₃/m space group with Z=2, a=13.308(3), c=21.092 (4) Å, V=3235(1) Å³. The structure of the complex cation consists of independent molecules with Hg pentacoordinated in exact trigonal bipyramidal geometry.     

[Pb2(TNR)(NO3)2(H2O)]的制备和晶体结构研究

[Pb₂(TNR)(NO₃)₂(H₂O)] was prepared by reaction of the aqueous solution of lead nitrate and magnesium styphnate. The crystal structure of Pb₂(TNR)(NO₃)₂(H₂O)was determined by single crystal diffraction analysis. The crystal is triclinic, space group P1 with crystal parameters a=0.7279(2)nm,b=1.0698(2)nm,c=1.0738(2)nm;α=86.82(1)°,β=89.52(2)°,γ=83.50(2)°;V=0.8295(3)nm³,Z=2,D_c=3.201g·cm^-3, F(000)=716. The final R value is 0.0358.In the crystal structure, one lead ion was represented by nine coor-dination geometry; the other was showed as ten coordination geometry.