α-氯代乙苯/TiCl4/Ti(OiPr)4引发β-蒎烯活性阳离子聚合

－４０℃条件下,在ＣＨ２Ｃｌ２溶剂中以α－氯代乙苯为引发剂,ＴｉＣｌ４和Ｔｉ（ＯｉＰｒ）４混合物为Ｌｅｗｉｓ酸活化剂,进行β－蒎烯阳离子聚合,单独使用强的Ｌｅｗｉｓ酸ＴｉＣｌ４时,聚合反应在瞬间完成,聚合产物的分子量分布较宽,添加本身无催化活性的弱Ｌｅｗｉｓ酸Ｔｉ（ＯｉＰｒ）４后,聚合反应减缓且聚合产物的分子量的分布变窄,当Ｔｉ（ＯｉＰｒ）４／ＴｉＣｌ４摩尔比为１／３时,产物的分子量随单体转化率线性增加,且分子量分布较窄,显示出活性聚合特性这种活性聚合特性由单体添加实验进一步得到证实。     

(Cp_2Ti)_2AlH_4CH_3,(Cp_2Ti)_2AlH_4Cl和(Cp_2Ti)_2AlH_4BH_4配合物的电子结构和催化活性

本文用CNDO方法研究了配合物(Cp_2Ti)_2AlH_4CH_3(Ⅰ),(Cp_2Ti)_2AlH_4Cl(Ⅱ)和(Cp_2Ti)_2AlH_4BH_4(Ⅲ)的电子结构和其催化活性的关系。结果表明,从Ⅰ到Ⅲ,随着Ⅹ吸电子能力增加,HOMO能量、在HOMO中氢桥骨架(Ti(μ-H)_2AlX(μ-H)_2Ti)成分、Al原子的电荷密度以及在LUMO中Ti原子成分均依次下降,但Ti—H键级依次上升,这些与在烯烃加氢和烯烃异构化反应中,Ⅰ的催化活性最强,Ⅱ其次,Ⅲ最弱这一实验结果相符。     

〆-氯代乙苯/TiCl_4/Ti(OiPr)_4引发β-蒎烯活性阳离子聚合

- 4 0℃条件下 ,在 CH2 Cl2 溶剂中以α-氯代乙苯为引发剂 ,Ti Cl4 和 Ti( Oi Pr) 4混合物为 Lewis酸活化剂 ,进行β-蒎烯阳离子聚合 .单独使用强的 Lewis酸 Ti Cl4 时 ,聚合反应在瞬间完成 ,聚合产物的分子量分布较宽 .添加本身无催化活性的弱 Lewis酸 Ti( Oi Pr) 4后 ,聚合反应减缓且聚合产物的分子量分布变窄 .当Ti( Oi Pr) 4/Ti Cl4 摩尔比为 1 /3时 ,产物的分子量随单体转化率线性增加 ,且分子量分布较窄 ,显示出活性聚合特性 .这种活性聚合特性由单体添加实验进一步得到证实     

Millimeter-wave rotational spectroscopy of FeCN (X 4Δi) and FeNC (X 6Δi): determining the lowest energy isomer

The pure rotational spectrum of FeCN has been recorded in the frequency range 140-500 GHz using millimeter/sub-millimeter direct absorption techniques. The species was created in an ac discharge of Fe(CO)(5) and cyanogen. Spectra of the (13)C, (54)Fe, and (57)Fe isotopologues were also measured, confirming the linear cyanide structure of this free radical. Lines originating from several Renner-Teller components in the ν(2) bending mode were also observed. Based on the observed spin-orbit pattern, the ground state of FeCN is (4)Δ(i), with small lambda-doubling splittings apparent in the Ω = 5/2, 3/2, and 1/2 components. In addition, a much weaker spectrum of the lowest spin-orbit component of FeNC, Ω = 9/2, was recorded; these data are consistent with the rotational parameters of previous optical studies. The data for FeCN were fit with a Hund's case (a) Hamiltonian and rotational, spin-orbit, spin-spin, and lambda-doubling parameters were determined. Rotational constants were also established from a case (c) analysis for the other isotopologues, excited vibronic states, and for FeNC. The r(0) bond lengths of FeCN were determined to be r(Fe-C) = 1.924 ? and r(C-N) = 1.157 ?, in agreement with theoretical predictions for the (4)Δ(i) state. These measurements indicate that FeCN is the lower energy isomer and is more stable than FeNC by ~1.9 kcal/mol.     

Ti2(OMe)4/SiO2催化剂的制备及其合成碳酸二甲酯的反应性能

采用表面改性和离子交换法制备了SiO2负载的Ti2(OMe)4双核桥联配合物催化剂，用IR、TPD和微反技术考察了催化剂的表面构造及CO2和CH3OH在催化剂表面上的化学吸附和反应性能。结果表明：双核桥联配合物Ti2(OMe)4以Ti-O-Si键锚定在SiO2表面上；CO2在催化剂表面存在桥式和甲氧碳酸酯基两种吸附态，其中甲氧碳酸酯基吸附态是生成DMC的关键物种；CH3OH在催化剂上只有一种分子吸附态。在150℃以下，CO2和CH3OH在Ti2(OMe)4/SiO2催化剂表面上高选择地生成碳酸二甲酯。     

催化剂体系R′Ti(OR)_nCl(4—n)-(烯烃)的EHMO的研究

在Zicglet-Natta型催化剂体系中,我们以烷氧基氯化钛Ti(OR)_nCl_(4-n)(全文中n=1,2,3,4)作为丙烯定向聚合的催化剂组份,发现随着取代基(—OR)数目的增加,催化活性逐渐降低。为了深入了解络合催化剂中配位体的改变对催化活性的影响,我们用EHMO方法对催化剂体系R′Ti(OR)_nCl_(4-n)-(烯烃)进行了理沦研究,得到了与实验结果相一致的结论。     

锂离子交换体Li1.5Ti1.625O4的研究(Ⅰ)——Li1.5Ti1.625O4的合成及锂的抽出/嵌入

以沉淀法合成了含锂及钛的复合氧化物Li1.5Ti1.625O4,并对其中Li+的抽出/嵌入进行了研究。通过X衍射、红外光谱(IR)、热重/差示(GT-DSC)等方法对各处理产物结构进行测试、表征,结果表明,所得产物具有尖晶石结构;在实验条件下,前驱体T750(Li)的盐酸处理产物T750(H)锂和钛的抽出率分别为88～97%和0.5～1.5%,且基本上保持了尖晶石的构造。     

A single source precursor for low temperature processing of nanocrystalline MgAl2O4 spinel: synthesis and characterization of [MgAl2(μ3-O)(μ2-O(i)Pr)4(O(i)Pr)2]4

A novel polynuclear single-source precursor was prepared and characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy. Nano-crystalline MgAl(2)O(4) spinel was synthesized via sol-gel processing of [MgAl(2)(μ(3)-O)(μ(2)-O(i)Pr)(4)(O(i)Pr)(2)](4). XRD, TGA-DSC and HRTEM confirmed the formation of a spinel phase at 475 °C, a temperature lower than any known processing temperature for MgAl(2)O(4).     

The conversion of multinuclear μ-oxo titanium(IV) species in the reaction of Ti(O(i)Bu)4 with branched organic acids; results of structural and spectroscopic studies

Crystalline materials have been synthesized in reactions of titanium(iv) tetraisobutoxide with branched organic acids (HOOCR', R' = CMe(2)Et, (t)Bu, CH(2)(t)Bu) in the molar ratio 1:1 at room temperature under Ar atmosphere. Particular attention has been paid to the structural and spectral characterization of metastable intermediate complexes of general formula [Ti(7)O(9)(O(i)Bu)(4)(HO(i)Bu)(OOCCMe(2)Et)(6)](2) (1) and [Ti(6)O(5)(O(i)Bu)(6)(OOC(t)Bu)(8)] (3), and their conversion towards more structurally stable compounds [Ti(6)O(6)(O(i)Bu)(6)(OOCC(Me)(2)Et)(6)] (2) and [Ti(6)O(6)(H(2)O)(2)(O(i)Bu)(6)(OOC(t)Bu)(6)] (4). The hexanuclear structure of (5) ([Ti(6)O(6)(O(i)Bu)(6)(OOCCH(2)(t)Bu)(6)]) has been postulated on the basis of IR and (13)C NMR spectroscopic data analysis. The possible reaction pathways which may occur during the formation of the above mentioned compounds are also discussed.     

手性BINOL/Ti(O~iPr)_4配合物催化辛炔对醛的不对称加成反应

利用手性联二萘酚/Ti(O~iPr)_4配合物作为催化剂,对辛炔对醛的不对称加成反应进行了研究。在该体系下,芳香醛、脂肪醛以及α,β-不饱和醛类底物都可通过该方法获取相应手性炔醇产物,并可取得中等至良好的对映选择性。     

The Oxalato-Titanium-Containing Tungstophosphate(V) Dimers, [Ti8(C2O4)8P2W18O76(H2O)4]18− and [Ti6(C2O4)4P4W32O124]20−

The oxalato-titanium(IV)-containing, dimeric 18-tungsto-2-phosphate [Ti₈(C₂O₄)₈P₂W₁₈O₇₆(H₂O)₄]^18? (1) and the 32-tungsto-4-phosphate [Ti₆(C₂O₄)₄P₄W₃₂O₁₂₄]^20? (2) are formed upon reaction of the oxalato-titanium complex [TiO(C₂O₄)₂]^2? with the trilacunary Keggin precursor [A-α-PW₉O₃₄]^9? and the hexalacunary Wells–Dawson precursor [H₂P₂W₁₂O₄₈]^12?, respectively. Polyanion 1 consists of two {PW₉} units encapsulating eight titanium centers and connected to each other via two Ti–O–Ti bridges, and crystallizes as a mixed potassium-sodium-lithium salt in the triclinic space group $P{\bar{1}}$ . Polyanion 2 comprises two {P₂W₁₆} units containing each two titanium atoms, and the two half-units are connected via two titanium atoms decorated by two oxalate groups each, and crystallizes as a mixed potassium-lithium salt in the rhombohedral space group $R{\bar{3}}c$ . Polyanions 1 and 2 were characterized in the solid state by single-crystal XRD, FT-IR, and TGA, whereas polyanion 2 was also investigated by ³¹P and ¹⁸³W NMR.     

{[Cu4(nip)4(4，4′-bipy)4(DMF)4]·CH3OH}n配合物的合成与晶体结构

A coordination polymer, {[Cu₄(nip)₄(4，4′-bipy)₄(DMF)₄]·CH₃OH}_n, have been synthesized by the layer method using 5-nitroisophthalic acid (H₂nip), Cu(CH₃COOH)₂ and 4,4′-bipyridine(4,4′-bipy) with three solutions in a marrow tube and structurally characterized by X-ray single-crystal structure analysis. The results indicated that the nip ligand has a μ₂ mono-atomic bridging-monodentate coordination mode and the structure is a two-dimensional network. CCDC: 623420.     

13C and1H NMR spectroscopic characterization of titanium(IV) alkylperoxo complexes Ti(OOtBu)n(OiPr)4?n with n=1, 2, 3, 4

Using¹³C and¹H NMR spectroscopy, titanium(IV) alkylperoxo complexes Ti(OOtBu)_n(OiPr)_4−n with n=1, 2, 3 and 4 were characterized in the reaction of Ti(OiPr)₄ withtBuOOH in CH₂Cl₂ and CDCl₃.     

锂离子交换体Li1.5Ti1.625O4的研究(Ⅱ)-H1.5Ti1.625O4的交换性能研究

本文就H1.5Ti1.625O4的pH滴定、分配系数Kd、交换容量、交换等温线、交换速度等离子交换性能进行了研究.研究结果表明,H1.5Ti1.62504对锂离子表现出很好的离子交换选择性及记忆性交换功能.     

Visible-light photoresponsive heterojunctions of (Nb–Ti–Si) and (Bi/Bi-O) nanoparticles

The increasing motivation to seek alternative sources of clean and sustainable energy has intensified, due to a growing awareness that fossil fuels are finite in quantity, and that the combustion products of such fuels contribute to global warming. Solar energy is considered one of the most readily available alternatives, but materials which are able to harness this form of energy need to be developed. This study details the development of a novel composite material, of the form of Bi/Bi-O nanoparticles supported on a (Nb–Ti–Si) oxide. Characterized using electrochemical and other methods, this material generates a photocurrent, and is capable of photo-oxidizing airborne-styrene in a fluidized-bed photoreactor when exposed to visible-light.     

物理化学综合实验:g-C3N4/MIL-125(Ti)的制备表征及其光催化还原Cr(Ⅵ)性能测试

该综合实验制备了一种负载型催化剂，并对其光催化还原Cr（Ⅵ）性能进行测试。采用溶剂热法制备g-C3N4/MIL-125（Ti）催化剂，通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、N2-吸脱附曲线、固体紫外-可见漫反射光谱（DRS）、荧光光谱（PL）及交流阻抗谱（EIS）表征了催化剂的结构、形态以及光催化性能。结合材料的表征数据及性能测试结果分析探讨g-C3N4的负载量对光催化还原Cr（Ⅵ）活性的影响，进一步探究该催化反应的进行机制。该实验实现了光催化技术与物理化学实验教学的结合，可让学生获取催化学科的前沿知识，了解催化反应以及各种现代测试技术的基本原理。     

溶胶-凝胶法制备高取向Bi4Ti3O12/SrTiO3(100)薄膜

Bi4Ti3O12具有良好的铁电、电光等性能山、特别是Bi4Ti3O12薄膜很适合作永久性存储材料，也可用于电光器件问．在微电子学、光电子学、集成光学、集成铁电学等领域均有广泛开发和应用前景，国外已用溅射法、激光沉积法制备出c轴取向Bi。Ti3Ol。薄膜【’，＼山东大学用MOCVD法制     

AQUEOUS PHASE SYNTHESIS OF(RC_5H_4)_2Ti(O_2CC_6H_4X)_2

Nine complexes(RC_5H_4)_2Ti(O_2CC_6H_4X)_2(R=H,CH_3;X=H,o-Cl,o-OH,o-NH_2,o-NHPh)have been conveniently prepared by the reaction of(RC_5H_4)_2TiCl_2 with 2 equiv.sodium salts of corresponding carboxylic acidin aqueous solution containing acetylacetone.The carboxylate ligands inthe complexes coordinate to titanium atom in monodentate mode.     

Ti—OEt bond cleavage in the reaction of Ti(OEt)4 with manganese carbonyl hydride. The new heterobimetallic complex [Ti3(OEt)6(μ2-OEt)3(μ3-OEt)2]+[Mn(CO)5]−

Titanium ethoxide, which is trimeric in organic solvents, reacts with HMn(CO)₅to eliminate ethanol and to form a heterobimetallic complex. The cationic part of the latter contains three titanium atoms bound by ₂- and ₃-OEt bridging groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1369–1372, August, 1993.