抗癌性钌配合物[HL][trans-Ru~ⅢCl_4L_2](L=2-NH_2-5-Me-STz)的水解机理

用量子化学密度泛函理论(DFT),并结合导体极化连续模型(CPCM)研究了具有潜在抗肿瘤活性的"Keppier型"钌配合物trans-[Ru~ⅢCl_4(2-NH_2-5-Me-STz)2](1)的水解反应过程.首先,在UB3LYP/(LanL2DZ+6-31G(d))理论水平上对水解反应中各平衡构型在气相条件下的有关结构进行全几何优化及振动频率分析;然后,在更高的基组水平LanL2DZ(f)+6-311HG(3df,2dp)上对优化的结构进行单点能计算,并考虑溶剂效应.计算得到水解反应过程中相应的结构特征和详细的反应势能面.对于第一步水解,液相中配合物1的活化能垒为92.9 kJ·mol~(-1),与已经报道的配合物trans.[Ru~ⅢCl_4(2-NH_2-Tz)_2](2)的活化能垒(96.3 kJ·mol~(-1))相接近,并与实验结果相符.对于第二步水解,反应在热力学上优先生成顺式双水解产物,恰如顺铂的水解反应机理一样,存在着所谓"顺式效应".即生成的顺式水解产物有利于其与生物分子靶标的键合,因此,顺式双水解产物在生物反应中有望成为重要的前体药物.本文研究结果有助于深入理解抗癌性Ru(Ⅲ)配合物与相关生物靶标的作用机理.     

抗癌性钌配合物[HL][trans-RuⅢCl4L2](L=4H-1，2，4-triazole)水解机理的理论研究

采用密度泛函理论(DFT)方法,并结合导体极化连续模型(CPCM)研究了具有抗肿瘤活性的"Keppler型"钌配合物[Htrz][trans-RuⅢCl4(4H-1,2,4-triazole)2](1)的水解反应过程。首先,在B1B95/(LanL2DZ+6-31G(d))理论水平上对水解反应中各平衡构型在气相条件下的有关结构进行全几何优化及振动频率分析。然后,在更高的基组水平LanL2DZ(f)+6-311++G(3df,2dp)上对优化的结构进行单点能计算,并考虑溶剂效应。计算得到水解反应过程中相应的结构特征和详细的反应势能面。对于第一步水解,水溶液中配合物1的活化能垒为116.6 kJ.mol-1,比已经报道的配合物[ImH][trans-RuⅢCl4(Im)2](ICR)的活化能垒高得多,进一步证实了降低含氮杂环中N原子碱性,可增强配合物在水溶液中的稳定性的水解规律。对于第二步水解,如同已经研究的多数"Keppler型"抗肿瘤钌配合物一样,反应在热力学上优先生成顺式双水解产物。     

2-（羟甲基）-N-甲基咪唑桥联Mn2ⅡMn2Ⅲ四核配合物的合成、结构和磁性简

报道了3个2-(羟甲基)-N-甲基咪唑(Hhmmi)桥联的Mn2ⅡMn2Ⅲ四核配合物[Mn4(hmmi)6(DMF)2·(N3)2](ClO4)2(1),[Mn4(hmmi)6(H2O)2(N3)2](ClO4)2(2)和[Mn4(hmmi)6Cl4]·6CH3CN(3·6CH3CN)的合成、晶体结构和磁性. 在配合物1~3中,中心结构皆为四核蝶形混合价Mn结构,2个MnⅡ占据蝶形两翼位置,2个MnⅢ占据蝶形中间位置. MnⅢ离子间通过hmmi-上的μ3-烷氧原子桥联,相应MnⅢ-O-MnⅢ键角为101.3°~103.4°;而MnⅢ-MnⅡ离子间通过hmmi-上的μ3-和μ2-烷氧原子桥联,相应MnⅢ-O-MnⅡ键角为92.5°~113.7°. 对配合物1~3进行变温磁化率拟合,结果表明,MnⅢ-MnⅢ间呈铁磁相互作用,而MnⅢ-MnⅡ间以及Mn4分子间存在较弱的铁磁或反铁磁耦合.     

杂环反铂(Ⅱ)抗癌药物水解反应机理的DFT研究

用DFT-B3LYP方法和IEF-PCM溶剂化模型研究了反铂抗癌药物trans-[PtCl2(piperidine)(Am)](Am=2-picoline(1),3-picoline(2),4-picoline(3)),trans-[PtCl2(piperidine)(piperazine)](4),trans-[PtCl2(pipera-zine)2](5)and trans-[PtCl2(iminoether)2](6)的水解过程.水解反应是药物与DNA靶分子作用的关键活化步骤.全优化和表征了一水解和二水解反应经由一般的SN2路径过程所有物种的势能面稳定点.结果发现反应过程遵循已经建立的平面正方形配合物的配体取代反应理论,即取代反应通常通过一个三角双锥过渡态结构的铂配体交换反应发生.得到的过渡态结构与以前的相关工作一致,所有反应都是吸热反应;所有体系的二水解能垒都高于一水解.与顺铂相比,这些配合物都有更快的水解反应速率;并与以前类似的反铂配合物的研究做了比较.研究结果提供了这些配合物水解反应过程的详细能量变化,对理解药物与DNA靶分子的作用机理和新型反铂抗癌药物的设计有帮助.     

两个Fe(II)配合物的合成、结构、磁性和穆斯堡尔谱 —— 配合物[Fe(dpq)(Mepy)2(NCS)2]的室温自旋交叉行为

设计制备了两个新的配合物[Fe(dpq)(Mepy)2(NCS)2](1)和[Fe(Medpq)(Mepy)2 (NCS)2](2)。室温下X衍射结果表明配合物（2）为正交晶系,晶胞参数为a = 15.057(3) Å, b = 14.569(3) Å, c = 13.180(3) Å, a = 90.00°, b=90.00°, g = 90.00°。[FeN6] 变型八面体构型中,两个NCS-与其顺式配位,其余四个氮分别来自Medpq和两个Mepy。变温磁化率和穆斯堡尔谱学的研究表明配合物（1）（2）存在自旋交叉,配合物（1）的自旋转换温度为 T1/2 =340K,而配合物（2）在低温条件下的转换是不完全的。     

草酰胺桥联双核铜配合物结构单元的从头算

运用Gaussian 94W量子化学程序包 ,采用LanL2DZ基组 ,对草酰胺桥联双核铜配 (聚 )合物结构单元Cu2 (oxen) (OH) 2 [H2 oxen =N ,N' 二 ( 2 胺乙基 )草酰胺 ](包括顺、反构型及其单、三重态电子组态 )进行从头算研究 ,探讨该配合物结构单元的稳定性 ,并从电荷布居及分子轨道组成等电子结构特征分析这种配合物反式三重态比较稳定的原因 .计算结果与实验规律相符合 .     

三维1,4-二-(4-羧基吡啶基)丁烷合铜(Ⅱ)、银(I)配合物的合成及晶体结构表征

利用1,4-二-(4-羧基吡啶基)丁烷(L)合成了铜(Ⅱ)、银(I)的配合物[[CuL(H2O)3]·2(H2O)·2(NO3)}n(1)、{[AgL]·(H2O)·     

含C16长碳链1，2－邻二萘醌－2－肟钌（Ⅱ）配合物的合成

通过三种构型的1，2－邻二萘醌－2－肟（2－nqo)钌（Ⅱ）羰基配合物trans, cis－（Ru(2-nqo)2(CO)2](1){(trans-NO,cis-O},cis-,trans-[Ru(2-nqo)2(CO)2] (2){cis-NO,trans-O}及cis,-cis-[Ru(2-nqo)2(CO)2](3){(cis-NO,cis-O)}的去羰 基取代反应，合成了含C16长碳链2-nqo钌（Ⅱ）配合物trans-,cis-[Ru(2-nqo)2 (CO)(spy)](4),cis-,trans-(Ru(2-nqo)2(CO)(spy)(5),cis-,cis-[Ru(2-nqo)2 (CO)(spy)](6)及trans-,trans-(Ru(2-nqo)2(spy)2](7){(trans-NO,trans-O)}。 对其进行了红外、紫外－可见质谱及核磁人振测试，并利用^1H-^1H偶合二维核磁 技术对核磁共振峰进行了指认。     

纳米Ag@SiO2核壳结构的表面等离子体共振效应对铕配合物的荧光增强作用

分别制备了二氧化硅壳层厚度为10、25和80 nm的三种Ag@SiO₂纳米粒子, 合成了铕与不同比例苯甲酸根(BA)的配合物、铕与1, 10-邻菲罗啉(phen)及2, 2''-联吡啶(bpy)的配合物, 并对其进行表征. 表征结果推测配合物的组成为Eu(BA)_nCl_3-n·2H₂O (n=1, 2, 3)、Eu(phen)Cl₃·2H₂O和Eu(bpy)Cl₃·2H₂O. 配合物的荧光光谱显示, 在加入Ag@SiO₂纳米粒子后, 复合物的荧光强度有不同程度的增加, 这可能是由于表面等离子体共振造成的. 不同硅壳厚度的Ag@SiO₂纳米粒子的荧光增强顺序是25 nm>80 nm>10 nm, 这表明二氧化硅核壳厚度约25 nm时有较强的表面等离子体共振效应. 此外, 在这些复合物中, Eu(phen)Cl₃·2H₂O复合物的增强效果是最强的, 而Eu(BA)_nCl_3-n·2H₂O的增强效果是最弱的. 在三个苯甲酸铕配合物中, Eu(BA)₃·2H₂O的增强效果最弱, 其他两个苯甲酸铕复合物增强效果相对较好. 原因可能是含氮配合物(Eu(phen)Cl₃·2H₂O和Eu(bpy)Cl₃·2H₂O)可以和Ag@SiO₂更好地成键, 而苯甲酸铕配合物和Ag@SiO₂纳米粒子的作用相对较弱. Ag@SiO₂纳米粒子有望应用于增强稀土材料的发光.     

M(bpy)_3~(2 )(M=Fe,Ru,Os)电子结构与相关性质

报导了对配合物M(bpy)2 M=Fe,Ru,Os)的量子化学密度泛函(DFT)法研究的结果.在B3LYP/LanL2DZ方法与基组的水平上进行计算 ,探讨M(bpy)32 的电子结构特征及相关性质 ,特别是中心原子对配合物的配位键长、光谱性质、电荷布居及化学稳定性等的影响规律 ,为该类配合物的合成 ,为分析光、电、催化作用机理提供理论参考.     

Hydrolysis Mechanism of the NAMI-A-type Antitumor Complex (HL)[trans-RuCl4L(dmso-S)] (L=1-methyl-1,2,4-triazole)

The hydrolysis process of Ru(III) complex (HL)[trans-RuCl₄L(dmso-S)] (L=1-methyl-1,2,4-triazole and dmso-S=S-dimethyl sulfoxide) (1), a potential antitumor complex similar to the well-known antitumor agent (Him)[trans-RuCl₄L(dmso-S)(im)] (NAMI-A, im=imidazole), was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. The structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.     

手性络合物[M(bpy)_2(phen)]~(2+)和[M(phen)_2(bpy)]~(2+)(M=Ru,Os)圆二色谱的理论解析

应用密度泛函理论,在B3LYP/LanL2DZ水平上对C2对称性的混配络合物[M(bpy)2(phen)]2+和[M(phen)2(bpy)]2+(M=Ru、Os;bpy=2,2'-bipyridine;phen=1,10-phenanthroline)在水溶液中的几何构型进行了优化,并用TDDFT/B3LYP方法和相同的基组计算了其激发能、旋转强度和振子强度,绘制了相应的圆二色谱(CD).在分析有关跃迁性质的基础上,对实验圆二色谱的谱带进行了明确的解析和指认,同时讨论了短波区激子裂分的规律性.结果表明:四种络合物在长波区(λ>320nm)的CD吸收带主要是由d-π*跃迁产生的荷移谱带;短波区(λ<320nm)则是配体上平行于长轴的π-π*跃迁产生的激子耦合带,且对于Λ构型表现为正的手性激子裂分.其中,[M(bpy)2(phen)]2+只显示出正负两个激子带,分属于联吡啶和邻菲咯啉配体;而[M(phen)2(bpy)]2+则有三个激子带,其中左侧的两个(一负一正)属于邻菲咯啉配体,右侧的正带则属于联吡啶配体.此外,尽管激子耦合属于远程相互作用,但用TDDFT计算的激子裂分样式仍是正确的.这些结论对于深入理解有...     

[M(Im)2X2]型配合物的Far-IR和Raman光谱的理论研究

本文用从头计算RHF和密度泛函B3LYP方法以及LanL2DZ，SDD和6-31G(d)基组计算了配合物M(Im)₂X₂ (Im=imidazole；M=Zn(Ⅱ)，Pd(Ⅱ)，Pt(Ⅱ)；X=F，Cl，Br，I)的几何构型以及Far-IR和Raman振动频率。计算结果表明，对Zn(Ⅱ)配合物而言,B3LYP/6-31G(d)方法得到的几何参数与实验值吻合得最好，B3LYP/SDD次之。在计算Far-IR和Raman振动频率时，发现采用6-31G(d)基组，两种方法计算的结果差别不大。对LanL2DZ和SDD基组而言，对计算结果影响较大的是理论方法，基组影响甚微，个别的振动频率基组影响较大，相比较而言，SDD基组得到的结果更好一些。本文所使用的两种计算方法都能得到与实验值比较吻合的结果，而用从头计算RHF方法计算的结果与实验值更接近一些。在此基础上，预测了Pd(Ⅱ)和Pt(Ⅱ)配合物的Far-IR和Raman振动频率。     

M(bpy)2+3(M=Fe,Ru,Os)电子结构与相关性质

报导了对配合物Ｍ（ｂｐｙ）＾２＋３（Ｍ＝Ｆｅ,Ｒｕ,Ｏｓ）的量子化学密度泛函法研究的结果。Ｂ３ＬＹＰ／ＬａｎＬ２ＤＺ方法与基组的水平上进行计算,探讨Ｍ（ｂｐｙ）＾２＋３电子结构特征及相关性质,特别是中心原子对配合物的配位键长、光谱性质,电荷布局及化学稳定性等的影响规律,为该类配合物的合成,为分析光、电、催化作用机理提供理论参考。     

Crystal structure, spectroscopic, magnetic and theoretical studies of [bis(hippurato)bis(benzimidazole)copper(II)] propanol 1/4hydrate

The novel ternary complex [Cu(hipp)₂(bim)₂]·PrOH·0.25H₂O (1) has been prepared and fully characterised by single crystal X-ray structure determination. The central copper(II) is coordinated by two O-donor atoms of the hippurate ions and by two N-atoms of the benzimidazole ligand with a tetrahedrally distorted square-planar geometry. The complex molecules, connected by hydrogen bonds into a 2D network, form a supramolecular structure. A theoretical DFT calculation performed by the UB3LYP method combined with the LanL2DZ basis set shows that all metal-ligand bonds are of the L → M type. The results of the spectroscopic, EPR and NIR–Vis–UV, as well as magnetic study are consistent with the structural data.     

Binding to DNA purine base and structure-activity relationship of a series of structurally related Ru(II) antitumor complexes: a theoretical study

The thermodynamics of the binding of a series of structurally related Ru(II) antitumor complexes, that is, alpha-[Ru(azpy)2Cl2] 1, beta-[Ru(azpy)2Cl2] 2, alpha-[Ru(azpy)(bpy)Cl2] 3, and cis-[Ru(bpy)2Cl2] 4 to DNA purine bases (gunine, adenine at N7 site) has been studied by using the DFT method. The binding of imine form of 9-methyladenine (9-MeAde) to the Ru(II) moiety in a didentate fashion via its N6 and N7 atoms was also considered. The geometrical structures of the DNA model base adducts were obtained at the B3LYP/(LanL2DZ + 6-31G(d)) level in vacuo. The following exact single-point energy calculations were performed at the B3LYP/(LanL2DZ(f)+6-311+G(2d, 2p)) level both in vacuo and in aqueous solution using the COSMO model. The bond dissociation enthalpies and free energies, reaction enthalpies and free energies both in the gas phase and in aqueous solution for all considered Ru(II)-DNA model base adducts were obtained from the computations. The calculated bond dissociation enthalpies and free energies allow us to build a binding affinity order for the considered Ru(II)-DNA model base adducts. The theoretical results show that the guanine N7 is a preferred site for this series of complexes and support such an experimental fact that alpha-[Ru(azpy)(bpy)(9-EtGua)H2O](2+) (3-(9-EtGua)) is isomerized to alpha'-[Ru(azpy)(bpy)(9-EtGua)H2O](2+) (3'-(9-EtGua)). On the basis of structural and thermodynamical characteristics, the possible structure-activity relationship was obtained, and the distinct difference in cytotoxicities of this series of structurally related antitumor complexes was explained theoretically.     

The reaction of copper(II) and 2-hydrazino-2-imidazoline leading to the in situ formation of bisimidazoline (biz). Crystal structure and vibrational spectroscopy of mixed-valence [Cu(biz)2][Cu2Br4] complex

The reaction of Cu(OH)₂ and 2-hydrazino-2-imidazoline hydrobromide surprisingly resulted in complex compound where Cu(II) ions are chelated by a new ligand, namely bisimidazoline (biz). As has been found in the X-ray analysis, the [Cu(biz)₂]²⁺ cations are accompanied by [Cu₂Br₄]²⁻ anions, which makes the whole compound of metal-mixed-valency type. Both ions are centrosymmetric and quasi-planar. The Cu(II) coordination environment is a rectangle with almost equal Cu–N bond lengths (1.984(3), 1.987(3) Å). The electrostatic interaction of both complex ions is strengthened by two strong N–H···Br and four weaker (C–H···Br, C–H···N) hydrogen bonds. The relatively simple IR and Raman spectra were interpreted with help of quantum calculations carried out at the B3LYP/LanL2DZ level. The characterization of computed normal vibrations and correlating observed bands is given in terms of approximate D_2h symmetry. The most intense band resulting from the Cu–N stretching vibration (B_3u) was located at 342 cm⁻¹, by ⁶³Cu and ⁶⁵Cu isotope substitution. The chemical reactions leading to the formation of presented compound are also proposed.     

Density functional theory/time-dependent DFT studies on the structures, trend in DNA-binding affinities, and spectral properties of complexes [Ru(bpy)2(p-R-pip)]2+ (R = -OH, -CH3, -H, -NO2)

Studies on the electronic structures and trend in DNA-binding affinities of a series of Ru(II) complexes [Ru(bpy)2(p-R-pip)]2+ (bpy = 2,2-bipyridine; pip = 2-phenylimidazo[4,5-f] [1,10]-phenanthroline; R = -OH, -CH3, -H, -NO2) 1-4 have been carried out, using the density functional theory (DFT) at the B3LYP/LanL2DZ level. The electronic absorption spectra of these complexes were also investigated using time-dependent DFT (TDDFT) at the B3LYP//LanL2DZ/6-31G level. The computational results show that the substituents on the parent ligand (pip) have a significant effect on the electronic structures of the complexes, in particular, on the energies of the lowest unoccupied molecular orbital (LUMO) and near some unoccupied molecular orbitals (LUMO+x, x = 1-4). With the increase in electron-withdrawing ability of the substituent in this series, the LUMO+x (x = 0-4) energies of the complexes are substantially reduced in order, for example, epsilon(LUMO)(1) approximately epsilon(LUMO)(2) > epsilon(LUMO)(3) > epsilon(LUMO)(4), whereas the pi-component populations of the LUMO+x (x = 0-4) are not substantially different. Combining the consideration of the bigger steric hindrance of complex 2, the trend in DNA-binding affinities (K(b)) of the complexes, that is, K(b)(2) < K(b)(1) < K(b)(3) < K(b)(4) can be reasonably explained. In addition, the experimental singlet metal-to-ligand charge transfer ((1)MLCT) spectra of these complexes can be well simulated and discussed by the TDDFT calculations.