杂多酸盐(TBA)n[XW9Mo2(CH3SiOSiCH3)O39]的合成和表征

具有Keggin衍生结构,以α-[SiW₁₁(RSiOSiR)O₃₉]^4-(R=C₂H₅、C₆H₅、NC(CH₂)₃、C₃H₅)为阴离子的杂多酸盐已有报道^[1],但以[XW₉Mo₂(RSiOSiR)O<     

四钼簇合物Mo4(μ3-O)2O4Cl2(OCOC6H5)6和[Mo4(μ3-O)2O4Cl2(OCOC6H4CH3)6]·2C 总被引：2，自引：0，他引：2

姜燕  樊玉国  孙春亭  李铁津 《无机化学学报》1990,6(3):261-266

含氮宾或卡宾的金属羰基簇合物的结构化学研究——Ⅰ.H2Fe3(N-C6H5)(CO)9和Fe3(N-C6H5)(μ3-CO)(CO)9的合成和结构

含氮宾的两个三核羰基铁簇合物是由[Et₃NH][HFe₃(CO)₁₁]与C₆H₅NCO在苯中反应获得.应用四园衍射仪测定了H₂Fe₃(N-C₆H₅)(CO)₉(Ⅰ)和Fe₃(N-C₆H₅)(μ₃-CO)(CO)₉(Ⅱ)的晶体结构.晶体数据为:C₁₅H₇NO₉Fe₃(Ⅰ),空间群P2₁/a,a=18.343(2),b=9.072(1),c=11.451(1)Å,β=102.03(1)°,V=1863.7ų,Z=4,D_c=2.143g/cm³;C₁₆H₅NO₁₀Fe₃(Ⅱ),空间群P2₁/c,a=8.634(1),b=13.026(1),c=17.642(2)Å,β=97.68(1)°,V=1966.3ų,Z=4,D_c=1.820g/cm结构系用直接法解出,最后R_Ⅰ因子为0.033,R_Ⅱ因子为0.027.测定结果表明,(Ⅰ)和(Ⅱ)分子均具有C_s对称性,且三个Fe原子共面,呈近似等边三角形结构.(Ⅰ)中面桥N原子以不对称方式与三个Fe原子成键;(Ⅱ)中面桥羰基以不对称方式与三个Fe原子键连.Fe-N和Fe-C键长分别在1.896-1.938Å和2.006-2.110Å之间.     

Mo4(μ3-S)3(μ3-O)[μ-S2P(OEt)2]3[S2P(OEt)2]3的晶体结构

用x射线衍射法测定了四核钼原子簇化合物Mo₄(μ₃-S)₃(μ₃-O)[μ-S₂P(OEt)₂]₃[S₂P(OEt)₃]的晶体结构。晶体属三种晶系。晶胞参数为a=13.387(3),b=13.997(4),c=16.281(3)Å,α=72.84(2)°,β=87.92(2)°,γ=84.87(2)°;z=2;空间群P1。由直接法(MULTAN—80)求得原子坐标。所有非氢原子坐标和热参数经全矩阵最小二乘方精修,最后偏离因子R=0.092。研究表明,在这一中性配位分子中,簇胳中心为[Mo₄S₃O]类立方烷构型,加上桥式和端式两种[S₂P(OEt)₂]^-配体,每个Mo原子周期都满足了畸变六配位八面体的要求。本文还讨论了两种[S₂P(OEt)₂]^-配体在结构参数上的差别。     

固相配位化学反应研究——ⅩⅩⅩⅩⅠ.[Co(NH3)5(H2O)]Br3,[Cr(NH3)5(H2O)](NO3)3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应动力学研究

本文主要用气相色谱逸出气体分析方法,借助于红外、紫外可见漫反射谱等手段研究了[Co(NH₃)₅(H₂O)]Br₃、[Cr(NH₃)₅(H₂O)](NO₃)₃与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应,计算了失水与失氨的动力学参数,发现第一步反应失水生成一取代中间产物,其活化能与外加阴离子无关,为S_N     

FTIR-ATR原位观测Mg(NO3)2气溶胶

利用FTIR-ATR(傅里叶变换红外-衰减全反射)原位光谱技术在分子水平上研究了ZnSe基底上Mg(NO₃)₂气溶胶颗粒的潮解和风化过程. 根据FTIR-ATR光谱的演变可知, Mg(NO₃)₂气溶胶在潮解过程中经历了复杂的相变: 相对湿度(relative humidity, RH)接近3%时, Mg(NO₃)₂气溶胶颗粒为无定型水合物; 稍微升高相对湿度, 无定型颗粒转化为Mg(NO₃)₂·nH₂O(n≤5)晶体, 并且在其表面逐渐形成热力学稳定的Mg(NO₃)₂·6H₂O晶体; 相对湿度达到Mg(NO₃)₂·6H₂O的饱和点(53% RH)时, Mg(NO₃)₂·6H₂O开始溶解, 同时, 内核Mg(NO₃)₂·nH₂O(n≤5)晶体在其表面持续转化为Mg(NO₃)₂·6H₂O晶体, 导致固态气溶胶颗粒全部潮解时的相对湿度延迟到76%. 风化过程中, Mg(NO₃)₂液滴随相对湿度的降低逐渐失水进入过饱和区域; 相对湿度降至5%以下时, 形成无定形颗粒. 在过饱和Mg(NO₃)₂液滴的FTIR-ATR光谱中, NO₃^-对称伸缩振动(v₁- NO₃^-)的吸收强度明显增加, 是溶剂共享离子对, 甚至接触离子对持续形成的结果.     

(CH3)3CO+NO反应机理的理论研究

用量子化学密度泛函方法, 在B3LYP/6-31G*水平下研究了叔丁基氧自由基(CH₃)₃CO和一氧化氮NO气体的反应机理. 研究表明, 该反应是在单、三态势能面上的多通道反应. 反应物经由中间体重新解离出(CH₃)₃CO与NO的反应通道的势能面最低, 单重态的势能面低于三重态的势能面, 反应以(CH₃)₃CONOÛ(CH₃)₃CO+NO为主. 正是这种反应平衡的存在使检测到(CH₃)₃CO自由基的几率增加; NO对 (CH₃)₃CO自由基有稳定化作用.     

羰基过渡金属异核原子簇(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的合成与表征

本文利用高压法制备HFe₂Co(CO)₉(μ₃-S),作为原料,经脱质子化作用,再分别与(PPh₃)₂Cu(NO₃)和PPh₃AuCl反应,将Ph₃Cu-或Ph₃Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh₃)₂CuFe₂Co(CO)₈(μ₃-S)和(PPh₃)₃AuFe₂Co(CO)₇(μ₃-S)的化合物.文中对此两个新化合物进行了IR,UV,¹H和³¹P NMR.元素分析、熔点测定等性质表征,并对(PPh₃)₂CuFe₂Co(CO)₇(μ₃-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe₂和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位.     

双核银配合物Ag2[Ph2P(CH2)2Ph2]4(NO3·CH3OH)2的合成和分子结构研究

The crystal of Ag₂[Ph₂(CH₂)₂Ph₂l₄(NO₃·CH₃OH)₂ is monoclinic, space group P2₁/n, with a=14.741, b= 19.042, c= 18.982Å;β = 110.66°. The molecule has a 2₁ symmetry axis. The four dppe ligands are coordinated in two ways, two ligands bridging the two silver atoms, and the other two ligands chelate to each silver atom separately to form two penta-cycles.     

(CH3)3CO + CO反应机理的理论研究

用量子化学密度泛函方法, 在B3LYP/6-31G^*水平下研究了叔丁基氧自由基(CH₃)₃CO和一氧化碳CO气体的反应机理. 为了得到更可靠的能量值, 在CCSD(T)/6-31++G^**水平下做了单点能计算. 研究表明, 该反应是一个多通道反应. (CH₃)₃CO自由基与CO作用主要生成(CH₃)₃C + CO₂. 这对于消除大气污染起到一定的作用.     

Ca3La3(BO3)5中Eu3+的光致发光

本文详细地研究了紫外光激发下,Ca_3La_3(BO_3)_5中Eu~(3+)的发光光谱和激发光谱与组成、结构的关系.发现Eu~(3+)在此基质中可能不止一个发光中心;Eu~(3+)自身浓度猝灭的机理为电四极-四极相互作用.     

MoO3 / Al2O3、MoO3 / TiO2与NiO-MoO3 / TiO2催化剂上活性相还原行为的XPS考察

The H_2 reduction behaviours of MoO_3/Al_2O_3, MoO_3/TiO_2 and NiO-MoO_3/TiO_2 samples prepared by impregnation method were studied at various temperatures for different times by XPS technique. The recored XPS spectra of Mo3d from those samples were treated by computer curve fittingprogram to measure the distribution of various molybdenum oxide species with different valence states. The results of computer fitting shows that there areMo(Ⅵ), Mo(Ⅴ)and Mo(Ⅳ) on the all of reduced samples. However, after H_2 reductonin same way, the percentage of low valence species Mo(V) and Mo(IV) on the MoO_3/TiO_2 is much higher than on the MoO_3/Al_2O3 (Fig.2). For example, after H_2 treatment at 500 ℃ for 2 hrs., Mo(IV) species on the surface of MoO_3/TiO_2 sample is about 60% and it is three times higher than what is found on the MoO_3/Al_2O_3 sample. In addition, the reduction of molybdena on TiO_2 support is much easier and faster than on Al_2O_3 support (Fig.3). Addition of NiO further promotes the reduction of molybdena to cause the strting reduction temperature producing Mo(IV) and Mo(V) to be decreased about 100 ℃. and 80% of molyb dena on NiO-MoO_3/TiO_2 support could be reduced to Mo(IV) (Fig.2). A detail discussion about the interaction between molybdena and carries was presented. It was suggested that TiO_2 is certainly involved in the reduction and oxidation process of molybdenum oxide species on the surface of it.     

CrO3在γ-Al2O3和SiO2载体表面的分散状态

用X光衍射(XRD)方法研究了CrO_3/SiO_2和CrO_3/γ-Al_2O_3体系。用相定量外推法测定活性组份在载体表面的最大分散量。在干燥气氛中将CrO_3与载体混合, 并在低于CrO_3熔点的温度下烘烤制备样品, 实验得到CrO_3在SiO_2或者γ-Al_2O_3表面的最大分散量都随温度的升高而增大。CrO_3在SiO_2表面的最大分散量由101 ℃的0.27gCrO_3/g SiO_2到170 ℃的0.38g CrO_3/g SiO_2; CrO_3在γ-Al_2O_3表面的最大分散量由120 ℃的0.22g CrO_3/g γ-Al_2O_3到171 ℃的0.42g CrO_3/g γ-Al_2O_3。CrO_3在SiO_2或γ-Al_2O_3表面的最大分散量超过密置单层量, 可由易聚合形成同多酸根来解释。     

Fe3(CO)8[P[SC6H5)Cl2](μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8 (P(SC_6H_5) Cl_2) (μ_3′-S)_2 was synthesised by reacting Fe_3(CO)_9 (μ_3-S)_2 with P (SC_6H_5) Cl_2. The crystal and molecular structure of the title compound has been determined by single crystal diffraction method. Crystal data: triclinic, space group P1, with a=0.7571(1), b=0.9097(1), c=1.7706(2) nm, α=95.03(1), β=101.79(1), γ=105.73(1)°, V =1.1359 nm, Z=2, Dc=1.935 g·cm~(-3). The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix least-squares with anisotropic thermal paramaters for non-hydrogen atoms, using 3724 observed reflections withI≥3σ(I). The final residual factor R=0.025, R_W=0.028.Fe_(CO)_8(P(SC_6H_5)Cl_2)(μ_3-s)_2 has a face-bridged 4e donors and the monosubstituted ligand is on the apical Fe atom.     

RbEuI3和CsEuI3的合成及结构与性质研究

本文用一步法合成了新合物ＲｂＥｕＩ３与ＣｓＥｕＩ３，测定了化合物的组成，结构，熔点，密度，荧光光谱，极谱电位及磁矩，确定了化合物中Ｅｕ的价态为正二价。     

MoO3负载在新型TiO2/γ-Al2O3载体上的表面状态与性质

MoO_3担载在TiO_2或γ-Al_2O_3载体上是一类重要的工业催比剂, 其表面状态和表面性质国内外已有过许多报导, 本文报导~[1-5], MoO_3负载在我们所研制的新型TiO_2/γ-Al_2O_3载体(指以γ-Al_2O_3为骨架, 表面上铺以TiO_2物种的载体)上的表面状态与性质。     

担载的Co2(CO)6(PBu3)2络合物的表面化学

红外光谱表明当Co_2(CO)_6(PBu_3)_2羰基络合物担载于不同的氧化物上后, 其羰基振动频带位置的波数顺序为: 络合物/SiO_2=络合物/TiO_2>络合物/Al_2O_3>络合物/ZrO_2。当这四种担载络合物在真空中加热脱羰基时, 以ZrO_2和Al_2O_3为载体者出现相当于桥式配位羰基的振动频带, 分别至300 ℃和200 ℃时羰基完全脱去。以TiO_2和SiO_2为载体者,基本没有出现桥羰基的频带, 而且在较低的温度下羰基即可脱去。紫外漫反射光谱表明担载络合物与担载前相比其表征Co-Co键和Co—Co配位键性质的特征带仍然存在, 脱羰基后出现相当于Co~(+2)或Co_3O_4的特征谱带。程序升温分解反应发现在H_2气氛中有表面加氢反应发生。     

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。     

膦桥多核银络合物[Ag4(dppe)3(NO3)4]的合成与结构

A new polynuclear silver complex with bridging diphorsphine ligand has been synthesized and characterized by :single cryatsl X-ray diffraction method The compound crystallizes in the triclinic space group P1 with a=1.27489, b=1.34715, c=1.47015 nm; α=59.747, β=63.949, γ=70.196°; V=1.9369 nm. The simplest formularis [Ag_4· dppe)_3(NO_3)_4], Mr=1874.79, D_c=1.607 g·cm~(-3), Dm=1.62 g·cm~(-3), μ(MoKa)=11.69 cm~(-1), F(OOO)=942. The structure was solved by conventional heavy-atom techniques and refined by full-matrix least squares to give discrepany indices of R=0.048 and RW=0.060(W=1/[σ(Fo)~2+(PWT*Fo)~2+QWT]-Fo) for 5052 reflections. An empirical absorption correction program DIFABS was performed.Silver atoms are linked by bridging ligands of dppe and nitrate, forming a network extending in space. Each structural unit contains two binuclear subunits, of which silver atoms are bridged by nitrates. The two subunits are connected by one dppe ligand. Silver atoms are not equivalent in subunit and one of the nitrates functions not only as a monodentate bridging ligand, but also as an asymmetric bidentate chelating lingand. All coordinate configurations of silver are shown as distorted tetrahedron.