三氯化钕异丙醇络合物的晶体结构和分子结构

本文报导了X射线衍射法确定的三氯化钕异丙醇络合物[NdCl₃·(CH₃CHOHCH₃)₃]₂的晶体结构。在晶体中每二个钕离子通过二个氯离子形成的氯桥相联,组成一个双核稀土络合物分子。其中每个Nd离子是七配位的。     

Ce(ph3PO)(DBM)2(NO3)2的合成与鉴定

β-二酮络合物已获得广泛而深入的研究,Ce(Ⅳ)的β-二酮类络合物的研究也有报导^[1-3].但是,关于Ce(Ⅳ)的β-二酮与其它混合配体络合物的研究至今未见报导.我们以(NH₄)₂Ce(NO₃)₆为起始物质,经由双-(三苯基氧化膦)硝酸铈(Ⅳ)中间络合物在混合溶剂中与DBM反应制得该化合物.通过紫外、红外光谱以及¹HNMR谱等研究,对该络合物的性质进行了讨论.     

稀土冠醚类络合物的研究(Ⅲ)——硝酸钪与邻苯二酮-17-冠-5及邻苯二酮-14-冠-4固态络合物的合成与性质

制得硝酸钪与两种冠醚的固态络合物,确定其组成为Sc(NO₃)₃·C₁₆H₂₀O₇·H₂O及Sc(NO₃)₃·C₁₄H₁₆O₆·H₂O。研究了冠醚本身及其钪的相应络合物的合成及有关性质。     

担载的Co2(CO)6(PBu3)2络合物的表面化学研究

本文采用红外光谱,紫外漫反射光谱,程序升温分解技术以及X-光电子能谱综合研究了Co₂(CO)(PBu₃)₂羰基络合物与Zr(OH)₄、ZrO₂、Al₂O₃、TiO₂和SiO₂等氧化物担体之间的相互作用及其在真空中加热分解和在He或H₂气流中的程序升温脱羰基过程。     

四氯化钼催化丁二烯1,2-聚合体系的紫外可见光谱研究

对四价钼系催化丁二烯1,2-聚合中Mo(Ⅳ)络合物的紫外可见光谱进行了研究.MoCl₄乙酸乙酯溶液呈棕红色,显顺磁性.在光谱的紫区和红区共有3个自旋允许d-d跃迁吸收带.Mo(Ⅳ)八面体络合物上各种配体的交换对光谱吸收带位置无影响.Mo(Ⅳ)在512nm处的特征吸收带随Al(i-Bu)₃/Mo或Al(i-Bu)₂OPh/Mo增加而渐趋消失,这是Mo(Ⅳ)→Mo(Ⅲ)反应的标志.在MoCl_4-n·(OC₈H₁₇)_n-Bd-Al(i-Bu)₂OPh₃组分陈化体系中Mo(Ⅳ)的还原得到加快,催化聚合活性亦有提高。     

电位法测定烟酸银络合物的稳定常数

在25℃、有2MKNO_s存在的条件下,用电位法测定银与烟酸络合物的稳定常数.测定结果:β₁=2.50×10²,β₂=1.38×10⁴.     

pH法研究UO2+2与甘氨酰替甘氨酸、白氨酸和四咪噻唑的络合物

本文应用pH法测定了UO₂⁺²与甘氨酰替甘氨酸、白氨酸和d,l-2,3,5,6-四氢-6-苯基咪唑[2,1-6]噻唑的络合物的逐级稳定常数,分别得出,UO₂⁺²-甘氨酰替甘氨酸体系:β₁=5.7×10³和β₂=1.4×10¹⁰;UO₂⁺²-白氨酸体系:β₁=4.0×10⁵和β₂=1.6×10¹³,以及UO₂⁺²-d,l-2,3,5,6-四氢-6-苯基咪唑(2,1-6)噻唑体系:β₁=6.5×10⁴和β₂=2.0×10¹⁰(25℃,μ=0.1,KCl维持)。同时,将徐光宪的溶液中络合物吸附平衡理论引入pH法研究络合物稳定常数中。     

锗－芦丁极谱络合吸附波的研究

在醋酸盐缓冲底液中,可获得Ge-芦丁的2个灵敏的络合吸附波P₁和P₂,分别对应于络合物中Ge(Ⅳ)还原至Ge(Ⅱ)再还原至Ge(0).两波的检出限分别为8.0×10^-8和4.0×10^-8mol/L.测得电活性络合物的组成为Ge:Rt=1:3,表面电极反应的速率常数(k_s)₁=10.5s^-1,(k_s)₂=1.9s^-1.还测定了有机锗口服液中锗的含量。     

化合物Al2Mo3-xWxO12的合成与结构

合成并表征了一系列化合物Al₂Mo_3-xW_xO₁₂ x=0,0.5,1.0,1.5和2.0的化合物是以单斜晶系Al₂(MoO₄)₃为基质的化合物和固溶体,空间群为P2₁/a;x=2.5和3.0的标题化合物是以正交晶系Al₂(WO₄)₃为基质的固溶体和化合物,空间群为Pbcn.利用粉末X射线衍射图谱全谱拟合的方法精修了x=0,0.5,1.0,1.5,2.0的标题化合物的结构,讨论其相变机理.     

亚硝酸三(乙二胺)合镍的合成和性质

关于三(乙二胺)合镍的亚硝酸盐,Bandyopadhayay^[1]曾使醋酸镍、亚硝酸钠和乙二胺作用,得到顺磁性物质Ni₂en₂(NO₂)₃(OH),并认为它是无机高聚物.Бабаева和张守纲^[2]在合成[Nien₂(NO₂)₂]络合物时,观察到紫红色晶体,认为是亚硝酸三(乙二胺)合镍,但未列出化学分析和性质测定的数据.我们用醋酸镍、亚硝酸钠和过量的乙二胺作用,合成亚硝酸三(乙二胺)合镍(Ⅱ),并测定其若干物理化学性质.     

苯并-15-冠-5的配位性能研究

苯并-15-冠-5苦味酸钠配合物单晶由丙酮-乙醇(1:1)溶液中得到,晶体属单斜空间群C_2h⁵-P₂₁/n,晶体学数据:a=11.134(3)Å,6=13.541(3)Å,c=14.927(4)Å,β=93.41(2)°Å,V=2246.4ų,Z=4,晶体结构由直接法解出,晶体结构分析结果表明,与苯环共轭的芳醚氧原子上的电子密度可通过苯环而转移。     

The Synthesis, Crystal and Molecular Structure of Tetrakis Dithiocarbamato Molybdenum(Ⅴ)Hexacloromolybdate

The title compound {Mo[S2CN( C2H5)2]4 1{MoCl6}-1 was synthesized,and its crystal structure was determined by X-ray diffraction.It is nionoclinic,space group P21/a with a=14.761(6)A b=16.012(6)A,c=17.108(9)A,β=102.63(4) and Z=4.The coordinates of a molybdenum atom were deduced from the Patterson function,and parameters of other atoms were found from successive Fourier syntheses.The block-diagonal least-siuares refinement for all alons gave final residual factors R=0.0908,Rw=0.0761.     

1:2型硝酸铀酰二苯并-18-冠-6氢键夹心式配合物的晶体结构

化合物[UO₂(NO₃)₂(H₂O)₂]·(DB18C6)₂晶体属单斜晶系,空间群为P21/k。晶体学参数:a=11.782(2)Å,b=8.584(2)Å,c=22.631(2),β=98.29(2)Å°,Z=2.用3024个I≥3σ(I)的三维X射线独立衍射数据进行结构解析,最终的R=0.066。结构分析表明,两个双齿配体硝酸根及两个水分子配位于线型铀酰离子的赤道平面上,铀的配位数是8,配位几何构型为稍有扭曲的六方双锥。配位水分子的4个氢原子分别与上下两层冠醚环上的氧原子生成氢键。形成夹心式分子缔合物。     

双(甲基环戊二烯基)二(2,6-二氯苯氧基)铪的晶体和分子结构

本文用X-射线衍射法测定了(η⁵CH₉C₅H₄)₅H₁(OC₆H₉Cl₃-2,6)₂的晶体和分子结构.晶体结构属单科晶系,空间群为P²1/c,晶胞参数为a=17.010(2)Å,b=8.577(1)Å,C=16.313(3)Å,β=101.52(3)°,晶胞内分子数Z=4.分子内有非结晶学二次旋转轴对称性,铪原子周围的两个甲基环戊二烯基和两个氧原子构成一个变形四面体.两个环戊二烯基的平面夹角为125.33°.氧-铪-氧键角为103.71°.铪-氧键长为2.004-2.022Å,较铪-氧单键键长为短,表明具有部分双键特性.     

18-冠-6钡与硫氰酸钴配合物的晶体和分子结构

用凝胶法培养了由18-冠-6钡与硫氰酸钴组成的配合物[Ba(C₁₂H₂₄O₆)·(H₂O)₂][Co(NCS)₄]的单晶。对配合物进行了熔点测定、元素分析和X-射线结构分析。     

Synthesis,crystal structure and thermal behavior of 4-amino-3,5-dinitropyrazole copper salt

A novel energetic combustion catalyst, 4-amino-3,S-dinitropyrazole copper salt （[Cu（adnp）2（H2O）2]）, was synthesized in a yield of 93.6% for the first time. The single crystal of [Cu（adnp）2（H2O）2] was determined by single crystal X-ray diffraction. It crystallizes in a triclinic system, space group p^-1 with crystal parameters a = 5.541（3） A, b = 7.926（4） A, c = 10.231（5） A,β = 101.372（8）°, V = 398.3（3） A3, Z = 1, μ = 1.467 mm^-1, F（0 0 0） = 243, and Dc = 2.000 g cm^-3. The thermal behavior and non-isothermal decomposition reaction kinetics of [Cu（adnp）2（H2O）2] were studied by means of different heating rate differential scanning calorimetry （DSC）. The kinetic equation of major exothermic decomposition reaction for [Cu（adnp）2（H2O）2] was obtained. The entropy of activation （△S≠）, enthalpy of activation （△H≠）, free energy of activation （△G≠）, the self-accelerating decomposition temperature （TSADT） and the critical temperature of thermal explosion （Tb） are 59.42 j mol^-1 K^-1, 169.5 kJ mol^-1, 1141.26 kJ mol ^-1 457.3 K and 468.1 K, respectively.     

A Unique Layered Cu-formate Hydrate of Cu(HCOO) 2·1/3H2O: Structures,Dehydration, and Thermal and Magnetic Properties

Anew layered Cu-formate hydrate of Cu(HCOO)₂·1/3H₂O is unique in its water content and the strongly waved (4,4) Cu-formate layers held by interlayer weak axial Cu-O_formate bonds and O-H_water···O_formate hydrogen bonds. The crystal is in orthorhombic space group Pbcn, with cell parameters at 80 K:a=7.9777(2) Å, b=7.3656(2) Å, c=21.0317(5) Å(1 Å=10⁻¹ nm), and V=1235.83(5) ų. The Cu²⁺ ions are in the environments of a square pyramid and elongated octahedron, in a ratio of 1/2 within the structure. In the layer, Cu²⁺ ions are connected by anti-anti formates via short basal Cu-O bonds. The structure remains unchanged until the dehydration that produces the layered anhydrous β-Cu(HCOO)₂, and the possible transformation mechanism, supported by diffraction evidence, is the reorganization of the Cu-O_formate bonds across the parent layers after dehydration. The two phases exhibit anisotropic thermal expansion behaviors closely relevant to the transverse thermal vibrations of the constituents. Cu(HCOO)₂·1/3H₂O is a 2-dimensional Heisenberg antiferromagnet, and exhibits a global spin-canted antiferromagnetism with the Néel temperature of 32.1 K. This is not only higher than that of the magnetically denser β-Cu(HCOO)₂, but also the highest among the copper formate frameworks.     

8-羟基喹啉(HQ)钇、镍离子加合物[YQ(HQ)2][NiQ3](ClO4)的合成及晶体结构

合成了标题化合物并测定其晶体结构,该晶体为单斜晶系,P21/c空间群,晶胞参数:a=16.972(4)Å,b=14.128(3)Å,c=22.615(4)Å,β=103.16(2)°,V=5280.14Å,F(000)=2264,Z=4。钇和镍均为六配位多面体取畸变八面体构型。讨论了[YQ(HQ)₂][NiQ₈](ClO₄)的红外光谱。     

Studies on Nucleophilic Ring-Opning Reaction of Ethylene Epoxide by (μ- CH3S)(μ-IMIgS) Fe2 (CO)6——Syntheais and Crystal Structure of (μ-Methylthio)- (μ- R -Hydroxylethylthio)hexacarbonyldiiron

A new type of Fe-S complex (C), (μ -CH₃S) (μ-HOCH₂CH₂S) Fe₂(CO)₆ which contains μ-β-hydroxyethyl, has been synthesized in high yield through ring-opening reaction of ethylene epoxide under uncleophilic attack of active complex (A), (μ-CH₃S)(μ-IMgS) Fe₂(CO)₆, followed byan alcoholysis of the intermediate (B). The crystal structure of (C) was determined by an X-ray diffraction technique. The crystal belongs to monoclinic system with space group of C₂/c. Cell parameters a= 15.784(3), b = 22.172(3), c=9.774(2)Å, β=119.53(2)°, V=2976.3ų. D_c = 1.80g cm^-3, Z=8, F(000)=1616 and final R=0.077.