蝎型钒氧配合物的合成、结构及量子化学研究

设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析.     

蝎型钒氧苯甲酸配合物的合成、结构及量化计算

设计合成了两种以聚吡唑硼酸盐、苯甲酸为配体的钒氧配合物VO[HB(pz)3](pzH)(C6H5COO)(1)和VO[HB(3,5-Me2pz)3](3,5-Me2pzH)(C6H5COO)(2)((HB(pz)3: 聚吡唑硼酸钠盐; pzH: 吡唑; HB(3,5-Me2pz)3: 聚甲基吡唑硼酸钠盐; 3,5-Me2pzH: 3,5-二甲基吡唑). 通过元素分析、红外光谱和X射线单晶衍射方法对配合物进行了表征. 并结合从头计算结果进一步分析了配合物的稳定性及分子中配键的共价特征. 分析结果表明, 配合物2的稳定性大于配合物1, 中心钒原子周围的价键类型都属于共价键范畴, 键序分析结果与晶体结构测定的键长结果是一致的.     

含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学

设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.     

蝎型铜配合物：Cu2[ μ-pz]2[HB(pz)3]2和Cu[B(pz)4]2的合成、结构及热分解动力学性质

本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu₂[ μ-pz]₂[HB(pz)₃]₂(1)和Cu[B(pz)₄]₂(2)(pz：吡唑(C₃H₄N₂))。运用元素分析、红外光谱对配合物进行了表征，并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明：配合物1的热分解反应分两步，配合物2的热分解反应一步进行。通过计算，配合物1热分解的第一步反应的可能机理为成核与生长，n=1/4；第二步反应的可能机理为化学反应。其非等温动力学方程分别为：dα/dT=A/β e^-E/RT·1/4(1-α)[-ln(1-α)]^-3和dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能分别是520.37 kJ·mol^-1和149.65 kJ·mol^-1；指前因子lnA分别是118.06 s^-1和28.10 s^-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为：dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能是111.41 kJ·mol^-1；指前因子lnA是21.20 s^-1。     

两个手性氧钒配合物[VO(Naph-Leu)(OMe)(CH3OH)] 和[VO(Naph-Phe)(OMe)(CH3OH)] 的合成、晶体结构和光谱表征

合成了2个新的手性L-亮氨酸萘酚醛和L-苯丙氨酸萘酚醛希夫碱氧钒配合物, [VO(Naph-Leu)(OMe)(CH₃OH)] (1)和[VO(Naph-Phe)(OMe)(CH₃OH)] (2)。X-射线单晶衍射分析表明, 1晶体属于正交晶系, P2₁2₁2空间群, 晶胞参数为:a=0.946 80(8) nm, b=3.246 3(3) nm, c=0.662 37(5) nm, V=2.035 9(3) nm³, Z=4, F(000)=864, R₁=0.046 3, wR₂=0.112 7, S=1.076。2晶体属于单斜晶系, P2₁空间群, 晶胞参数为:a=1.113 41(11) nm, b=0.724 09(6) nm, c=1.342 99(12) nm, V=1.047 95(16) nm³, Z=2, F(000)=464, R₁=0.035 8, wR₂=0.088 8, S=1.024。测定了它们的红外光谱、紫外光谱和圆二色光谱, 讨论了紫外吸收光谱和圆二色光谱性质。     

两个手性氧钒配合物[VO(Naph-Leu)(OMe)(CH3OH)]和[VO(Naph-Phe)(OMe)(CH3OH)]的合成、晶体结构和光谱表征

合成了2个新的手性L-亮氨酸萘酚醛和L-苯丙氨酸萘酚醛希夫碱氧钒配合物,[VO(Naph-Leu)(OMe)(CH3OH)](1)和[VO(Naph-Phe)(OMe)(CH3OH)](2)。X-射线单晶衍射分析表明,1晶体属于正交晶系,P21212空间群,晶胞参数为:a=0.946 80(8)nm,b=3.246 3(3)nm,c=0.662 37(5)nm,V=2.035 9(3)nm3,Z=4,F(000)=864,R1=0.046 3,wR2=0.112 7,S=1.076。2晶体属于单斜晶系,P21空间群,晶胞参数为:a=1.113 41(11)nm,b=0.724 09(6)nm,c=1.342 99(12)nm,V=1.047 95(16)nm3,Z=2,F(000)=464,R1=0.035 8,wR2=0.088 8,S=1.024。测定了它们的红外光谱、紫外光谱和圆二色光谱,讨论了紫外吸收光谱和圆二色光谱性质。     

钒氧配合物的合成、结构、性质及其细胞毒作用

钒氧配合物的合成、结构、性质及其细胞毒作用;钒氧配合物;三聚吡唑硼酸盐;细胞毒作用     

NTO镉(Ⅱ)配合物的合成、结构及量子化学研究

通过3-硝基-1,2,4-三唑-5-酮(NTO)与碳酸镉反应, 合成了标题配合物[Cd(NTO)₄Cd(H₂O)6]·4H₂O. 其结构用单晶分析法测定. 所得晶体学参数为a = 2.1229(3), b = 0.6261(8), c = 2.1165(3) nm, β = 90.602(3)°, V = 2.977(6) nm³, Z = 4, D_c = 2.055 g·cm^-3, μ = 15.45 cm^-1, F(000) = 1824; 晶体属单斜晶系, 空间群为C2/c, 由2523个F₀ > 4σ(F₀)的可观察衍射点用于结构解析和修正, 数据经吸收修正, 并经Lp因子校正. 最终偏离因子R = 0.0282, wR = 0.0792. 晶体测定结果表明, 在一个晶胞中存在两种类型的配位金属镉原子, 它们分别与4个NTO负离子和6个水分子配位, 形成以Cd原子为中心的四面体和四方双锥结构的双核配合物. 根据实验构型运用SCF-PM3-MO方法计算了3-硝基-1,2,4-三唑-5-酮(NTO)的镉配合物的电子结构, 计算结果表明, 当[Cd(NTO)₄Cd(H₂O)₆]·4H₂O加热至分解时, 最先失去吸附水, 其次是配位水, 当加热至NTO^-分解时, 硝基首先失去. 从定域分子轨道能级和组成可知, 2个Cd²⁺都主要以5S AO轨道进行配位成键.     

功能性咪唑基钒氧配合物的合成、结构与仿生催化

在室温条件下,甲醇体系中设计合成了一种新的以咪唑为配体的功能性钒氧配合物VO(imidazole)₄(SO₄)·H₂O(1)。 进行了元素分析、红外光谱表征,并用X-ray单晶衍射法测定了配合物1的晶体结构。 配合物1的晶体属于正交晶系,空间群:Pna2₁,a=1.384 4(3) nm,b=0.978 6(2) nm,c=1.361 7(3) nm,α=β=γ=90°,V=1.844 7(6) nm3,Z=4。 对配合物1的溴化催化活性进行了研究,通过实验得到了对苯酚红催化溴化的反应速率常数k=2.760 0×10⁷ L²/(mol²·s)。 讨论了配合物1的热稳定性,并结合从头计算结果进一步分析了配合物的稳定性及分子中配键的共价特征。 分析结果表明,V-O1的键序(1.055 3)明显要比V-O2(0.394 2)的键序大,V-N键序接近(0.333 6～0.341 9),配合物1的中心钒原子周围的价键类型均属于共价键范畴,键序分析结果与晶体结构测定的键长结果一致。     

氯化二(羟胺根)·(羟胺—O)·水合氧钒(Ⅴ)[VO·(NH2O)2·(NH3O)·H2O]Cl的晶体结构

调节硫酸氧钒与盐酸羟胺溶液至pH～4制得的题目晶体属空间群P2₁/n,晶胞参数a=8.201,b=8.597,c=9.947A,β=93.00°,Z=4.结构解出精修后R因子为0.069.结果表明,不对称单位中二个羟胺根以侧接态与VO³⁺配位,另一羟胺取端接态以O占据V的第五赤道配位位置,配位水处于氧钒基强键反位,Cl^-则在配阳离子界外以平衡电荷,晶体对的化学式确证为[(VO³⁺)(NH₂O^-)₂(NH₃O)(H₂O)][Cl^-]     

Insulin-like model complexes: Synthesis,spectra characterization and crystal structure of two novel oxovanadium complexes with poly(pyrazolyl)borate ligands VO(HB(pz)3)(H2B(pz)2) and VO(B(pz)4)2

Two new oxovanadium (IV) complexes VO(HB(pz)₃)(H₂B(pz)₂) (1) and VO(B(pz)₄)₂ (2) have been obtained by the reaction of oxovanadium sulfate with the corresponding ligands KHB(pz)₃, KH₂B(pz)₂ and KB(pz)₄, respectively. The two complexes were characterized by elemental analyses, IR, UV–Vis and X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group, Pca2₁. Complex 2 crystallizes in the orthorhombic space group, Pna2₁. In both complexes, five nitrogen atoms and one oxygen atom coordinate to the vanadium atom, forming a distorted octahedral geometry (VON₅). In addition, related spectra characterization, hydrogen-binding properties, structural configuration and quantum chemistry calculations are also discussed.     

Synthesis,Crystal Structure and Quantum Chemistry of the Complex [Cu（p-FBA）_2（phen）（H_2O）]

A novel metal-organic complex Cu(p-FBA)2(phen)(H2O) (p-FBA = p-fluorobenzoic acid,phen = 1,10-phenanthroline) has been synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analysis and IR spectra. The crystal belongs to triclinic,space group P1 with a = 7.8043(7),b = 10.4069(9),c = 14.3658(13) ,α = 105.3170(10),β = 96.877(2),γ = 96.7580(10)o,V = 1103.56(17) 3,Mr = 539.96,Z = 2,Dc = 1.625 g/cm3,μ = 1.050 mm-1,F(000) = 550,the final R = 0.0324 and wR = 0.0952. In the crystal,the structure consists of discrete molecules containing a five-coordinate copper(Ⅱ ) in a distorted square pyramidal configuration. Intramolecular O-H···O hydrogen bonds,weak intermolecular C-H···O hydrogen bonds and π-π stacking link the molecules into a one-dimensional chain structure. The study on the title complex has been performed with quantum chemistry calculation by means of G03W package on the Lanl2dz basis set. The stabilities of the complex together with the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated.     

Synthesis and ethylene polymerization behavior of {MeB(3-Ph-pyrazolyl)3}TiCl3

The new methyl-tris(pyrazolyl)borate reagents Li[MeTp^Ph] (1) [MeTp^Ph]⁻ = MeB(3-Ph-pyrazolyl)₃⁻) and Tl[MeTp^Ph] (2) react with TiCl₄ to afford (MeTp^Ph)TiCl₃ (3) in 77% and 81% yield respectively. 2 reacts with ZrCl₄ and HfCl₄ to yield mixtures of products. The reaction of 1 with TiCl₃(THF)₃ proceeds with B-N bond cleavage to afford TiCl₃(3-Ph-pyrazole)(THF)₂ as the major product (30%). The reaction of 3 with MeLi (3 equiv) yields 1 (60%) and reduced Ti species, via apparent displacement of [MeTp^Ph]⁻ and generation of unstable TiCl₄Me_4−x species. Under MAO activation conditions (MAO = methylalumoxane), 3 polymerizes ethylene to linear polyethylene. 3/MAO is significantly more active in ethylene polymerization than the hydrido-tris(pyrazolyl)borate analogue {HB(3-Ph-pyrazolyl)₃}TiCl₃/MAO.     

Synthesis and characterization of uranium(III) compounds supported by the hydrotris(3,5-dimethyl-pyrazolyl)borate ligand: Crystal structures of [U(Tp)2(X)] complexes (X = OC6H2-2,4,6-Me3, dmpz, Cl)

Reaction of [U(Tp^Me2)₂(NR₂)] (R = Ph, SiMe₃) with protic substrates such as 2,4,6-trimethylphenol (HOC₆H₂-2,4,6-Me₃), 3,5-dimethylpyrazole (Hdmpz), 2-mercaptopyridine (HSC₅H₄N) and phenylacetylene (HCCPh) afforded the corresponding [U(Tp^Me2)₂(OAr)] (Ar = C₆H₂-2,4,6-Me₃) (1), [U(Tp^Me2)₂(dmpz)] (2), [U(Tp^Me2)₂(η²-SC₅H₄N)] (3), and [U(Tp^Me2)₂(CCPh)] (4) compounds. Reaction of [U(Tp^Me2)₂(NR₂)] with Me₃SnCl or Me₃SiBr gave [U(Tp^Me2)₂Cl] (5) and [U(Tp^Me2)₂Br] (6), respectively, in high yield. The amido precursors failed to react with cyclopentadiene, but metathesis of [U(Tp^Me2)₂I] with NaCp yielded [U(κ³-Tp^Me2)(κ²-Tp^Me2)(η⁵-Cp)] (7). Thermolysis of 7 resulted in oxidation of the metal centre and redistribution of the ligands, giving [UCp₃(dmpz)] (8), pyrazabole (9) and [U(Tp^Me2)(dmpz)₃] (10). The complexes have been fully characterized by spectroscopic methods and the structures of 1, 2, and 5 were confirmed by X-ray crystallographic studies. In the solid state the complexes exhibit distorted pentagonal bipyramidal geometries.     

一个新的锡硫配合物(Et4N)[Sn2I6SOCH3]的合成、结构及量子化学研究

以锡粉、碘粉、硫粉和四乙基碘化铵为原料,在无水甲醇中,通过溶剂热反应合成了1个新的锡髧配合物(Et4N)[Sn2I6SOCH3]。对其进行了X-射线单晶衍射、元素分析的表征以及量子化学研究。该化合物属于单斜晶系,空间群为P21,a=0.728 65 nm,b=1.836 81 nm,c=1.016 25 nm,β=107.209°,V=1.299 2 nm3,Z=2。结构分析表明,化合物中的阴离子[Sn2I6SOCH3]-是由2个共边的SnSI3O三角双锥组成。电荷分布和前沿轨道的组成充分证实了配合物中配位键的存在。