【作者】 郝青丽；

【导师】 陆路德； 汪信； 杨绪杰；

【作者基本信息】 南京理工大学 ， 应用化学， 2004， 博士

【摘要】 论文以五硫化二磷和醇或酚类化合物为主要原料，通过固—液和固—固反应合成了一系列新的含有P、S、O和N的过渡金属配合物，即O，O’—二烷基二硫代磷酸和O，O’—二芳基二硫代磷酸金属配合物，及其与中性配体的混配物。取代基涉及了乙基、异丙基、环己基、氯乙基、烯丙基、苄基、苯基、对甲苯基、对氯苯基、α—萘基、2，4—二硝基苯基十一种；用到的含氮或其它配位原子的中性配体有：咪唑（Im）、吡啶（Py）、α—氨基吡啶（Apy）、2，2’—联吡啶（2BiPy）、4，4’—联吡啶（4BiPy）、乙二胺（En）、1，10—菲咯啉（Phen）和三苯基膦（PPh₃）七类。采用元素分析、红外光谱、UV—vis电子光谱、核磁共振技术和热分析的分析手段对合成的产物进行了表征。 借助单晶X射线衍射技术，解析合成的配合物的单晶结构，并首次报道了其中的九种配合物的晶体结构。 配合物[Ni（p-tolyl₂-DTP）₂Phen]的晶系是三斜，空间群是P（-）1，晶胞参数α=1.11819（2）nm，b=1.20934（2）nm，c=1.72860（2）nm，α=107.693（1）°，β=96.349（1）°，γ=109.896（1）°，d_calcd=1.401Mg／m³，Z=2。Ni是六配位的，六个配位原子分别来自两个DTP二齿配体的四个S原子和邻菲咯啉配体中的两个N原子。整个配合物的分子呈现出围绕在中心Ni原子周围的扭曲的八面体几何构型。 {[Cu（Ⅱ）（En）₂]（Et₂-DTP）₂}的晶系是单斜，空间群为P21／c，晶胞参数α=1.46683（3）nm，b=0.69409（1）nm，c=1.35889（1）nm，α=90°，β=111.157（1）°，γ=90°，d_calcd=1.426Mg／m³，Z=2。铜（Ⅱ）分别和来自两个乙二胺的四个氮原子构成相同的Cu-N键，形成了两个以Cu（Ⅱ）为中心呈四边形构型的CuN4。分子中的dtp作为阴离子中和分子中配位中心的二价铜。分子内存在着N-H…S型分子氢键。 {[Ni（Im）₆]（iPr₂-DTP）₂}分子处于单斜晶系，空间群为C 2／c，α=2.47585（4）nm，b=1.14460（2）nm，c=1.65815（1）nm，α=90°，β=112.689（1）°，γ=90°。Z=4，d_calcd=1.369 Mg／m³。Ni（Ⅱ）位于对称的八面体的六咪唑合镍中心，外围分布着两个一价的O，O’—二异丙基二硫代磷酸根离子。晶胞堆积中存在着N-H…S型分子内氢键、分子间氢键和S2…S2型分子间作用力。 双核配合物[Ag₂（allyl₂-DTP）₂（Phen）₂]的晶系是单斜，空间群为P1，晶胞参数α=0.9828（2）nm，b=1.0950（2）nm，c=1.1187（2）nm，α=68.31（3）°，β=74.95（3）°，γ=65.05（3）°，Z=2。二聚物的晶体结构中，每个银原子分别与来自Phen的两个N原子和来自两个O，O’—二（烯丙基）二硫代磷酸配体的两个S原子配位，形成中文摘要博士论文了四面体构型;同时两个银原子相互作用形成Ag一Ag弱的作用力一‘（键），从而整个分子呈现双四面体几何构型SZNZAg--A叨252。 [Ni（iPrZ一DTP）2（APy）21晶系单斜，空间群为p 21/n，晶胞参数a=0.66296（1）nm，b=1 .63605（2）nm，c=1.46386（2）nm，a=900，刀=99.938（l）o，尹=900，Z=20Ni（n）离子位于配位中心NINZS4的对称中心，生色团NINZS4的晶体构型是八面体几何构型。 [Zn(功（iPrZ一DTP）ZPhen]单斜晶系，CZ/c空间群。晶胞参数a=1 .93 15（4）nm，b== 1 .0438（2）nm，c=1.6567（3）nm，a=900，刀=102.89（3）“，夕=900，Z=4。Zll（11）原子周围有两个来自邻菲咯琳（P hen）的N原子和分别来自两个口，a一二异丙基二硫代磷酸根（D仰）的S原子与其配位成键，四配位的Zn的配位环境呈现的是扭曲的四面体几何构型。 配合物[M(功（iPr-D开）ZPhen]（M=Ni、Cd、FC）均结晶在正交晶系，空间群为Pbcn，Z二4。M（n）是六配位的，分别与来自两个DTP配体的四个S原子和来自Phen的两个N原子配位成键形成MNZS4的生色团，配合物是扭曲的八面体几何构型。 最后，借助金黄色葡萄球菌、大肠杆菌和枯草杆菌，测定了.口，口’一二取代基二硫代磷酸金属配合物及其与中性配体的混配物的杀菌活性。 关键词:二取代基二硫代磷酸金属配合物，合成，晶体结构，表征，杀菌活性更多还原

【Abstract】 Novel coordination compounds containing P, S, O, N atoms, named transition metal 0,0’- di-substituent dithiophosphates and their mixed complexes with neutral ligands, have been synthesized by the main reactants of P2S5 and alcohol or phenols through solid-liquid phase and solid-solid phase reactions. The used substituents cover iso-propyl (iPr), ethyl (Et), cyclohexyl, allyl, p-tolyl, benzyl (Ph); p-chlorophenyl, 2,4-di-nitrophenyl, a-naphthyl; the neutral ligands containing nitron or other coordination atoms consist of imidazole (Im), pyridine (Py), a-aminopyridine (Apy), 2, 2’-bipyridine (2BiPy), 4, 4’-bipyridine (4BiPy), 1, 10-phenanthroline (Phen), ethylenediamine (En), and triphenylphosphine (PPh3). Metal O, O’ -di-substituent dithiophosphates and their mixed complexes were characterized by Infrared spectra (IR), elemental analysis (EA), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and ultraviolet-visible (UV-vis) spectrophotometry analysis. Single crystals have been determinated by means of X-ray single crystal diffraction, among twenty two sorts of single crystals, nine structures of new complexes with mixed ligands were first reported. The main results were studied as follows:[Ni(p-tolyl2-DTP)2Phen] cystallizes as green prisms in the triclinic crystal system, space group P(-)l, with unit cell parameters a = 1.11819(2) nm, b = 1.20934(2) nm, c = 1.72860(2) nm, α = 107.693(1)°, β= 96.349(1)°, γ= 109.896(1)°. The calculated density is 1.401 Mg/m3 for Z = 2 molecules/unit cell. Nickel atom is coordinated through four S atoms from DTP groups and two N atoms from Phen, forming a distorted octahedron.Blue prisms of {[Cu(n)(En)2](Et2-DTP)2} were crystallized in the monoclinic crystal system, space group of P21/c, with unit cell parameters a = 1.46683(3) nm, b = 0.69409(1) nm, c = 1.35889(1) nm, α= 90°, β= 111.157(1)°, γ=90°. The calculated density is 1.426 Mg/m3 for Z = 2 molecules per unit. Chelated to the copper atom through four N atom are two ethylenediamine groups, forming a square geometry of CuN4. The DTP groups of molecule around the coordination center neutralize the charge of Cu (E) as anions. A network structure of {[Cu(II)(En)2](Et-DTP)2} is formed through the intermolecular hydrogen bonds of N-H ...S.The compound of {[Ni(Im)6](iPr2-DTP)2} crystallizes in the monoclinic spacegroup C 2/c, with a = 2.47585(4) nm, b = 1.14460(2) nm,c = 1.65815(1) nm, α= 90°, β= 112.689(1)°, γ= 90°, Z=4, and calculated density 1.369 Mg/m3 at 293 (2) K. The coordination around the Ni atom, located in an inversion center, is octhaheral with all positions being occupied by tertiary N atoms of the imidazole moieties. Two O, O ’-diisopropyl dithiophosphorous anions lie around the NiN6 center.The dimeric compound of [Ag2(allyl2-DTP)2(Phen)2] forms colorless multihydrogen in the monoclinic space group P1, with unit cell parameters a = 0.9828(2) nm,. b = 1.0950(2) nm, c = 1.1187(2) nm, a= 68.31(3)°, β= 74.95(3)°, γ= 65.05(3)°, Z = 2. The crystal structure is comprised of one independent dimer containing two coordination centers. Each Ag atom is coordinated through one of two S atoms from one DTP groups, respectively, and two N atoms from Phen. A double tetrahedral geometry of S2N2Ag-AgN2S2 is bridged through the weak silver-silver interaction.The crystalline compound [Ni(/Pr2-DTP)2(Apy)2] is formed in the monoclinic space group P21/n, with unit cell parameters a = 0.66296(1) nm, b = 1.63605(2) nm, c = 1.46386(2) nm, α= 90°, β = 99.938(1)°, γ = 90°, Z = 2. The Ni atom is located in the coordination center of the chromophore, NiN2S4, forming an octahedral geometry.The complex [Zn(n)(/Pr2-DTP)2Phen] is crystallized in the monoclinic space group C2/c. The unit cell parameters are a = 1.9315(4) nm, b = 1.0438(2) nm, c = 1.6567(3) nm, α= 90°, β= 102.89(3)°, γ= 90°, and the calculated density 1.371 Mg/m3 (for Z = 4). The four-coordinated Zn atom is bonded to two N atoms from the Phen ligand and two S atoms from two DTP groups, leading to the disto更多还原