向日葵（Helianthus annuus L.）种质资源的RAPD标记研究与应用

向日葵原产北美，通过人工培育，在不同生境上形成许多品种，具有丰富的遗传多态性，是一种集观赏植物、药用植物、油料作物于一体，经济价值很高的资源植物，产量高，具有较强的适应性。运用现代生物技术加强对向日葵种质资源的开发和保护，开展遗传多样性分析，加速新品种的选育，是当前向日葵研究工作的重点。随着现代生物技术的发展，从分子水平检测生物的遗传多态性已成为现实。本论文以向日葵生产中使用的基因型为实验材料，使用RAPD技术在向日葵种质资源遗传多态性分析以及向日葵杂交种种子纯度鉴定两方面进行了探讨。 采用RAPD 技术对我国21个向日葵基因型和11个国外的向葵基因型的遗传多态性进行分析。从80个10碱基随机引物中筛选出25个有效引物，在32个基因型中共扩增出188条DNA片段，其中164条带具有遗传多态性，约占总数的87.2%。使用NTSYS软件计算32个基因型间的Nei氏相似性系数，在此基础上通过非加权配对算术平均法（UPGMA）聚类，将32个向日葵基因型明显地聚成A、B两大类群。A类群包括21个国内向日葵基因型，并聚成了A1、A2二个亚类。B类群包括11个国外向日葵基因型，并划分为B1、B2两个亚类。根据聚类结果作出的遗传树谱图反映了所研究的向日葵基因型的亲缘关系。 在杂交种A15种子纯度鉴定中，从180个RAPD随机引物中扩增筛选出3个可将亲本和子代区分开的引物OPD09、OPD12和OPK12。OPD09产生亲本互补的特征带OPD09-1470bp、OPD09-870bp;OPD12产生母本特征带OPD12-1230bp，OPK12产生父本特征带OPK12-1540bp、OPK12-940bp，上述谱带均在子代中出现。以单引物（OPD09）和双引物（OPD12和OPK12）产生的这两组特征谱带作为分子标记分别对杂交油葵种子纯度进行鉴定得到了一致的结果，并与大田纯度检测结果基本符合。 实践表明，用RAPD对向日葵种质资源进行分析是可行的。

环戊二烯基轻稀土氯化物的合成及其稳定性的研究

I LnCl_3-LiCl-THF配合物的研究深入地研究了氯化稀土和氯化锂于四氢呋喃溶液中，以不同的摩尔比，在不同条件下的反应。实验结果表明，反应速度随着稀土元素原子半径的减小，LiCl/LnCl_3摩尔比的增大，以及四氢呋喃用量的增加而加快。通过紫外质谱元素分析和X-射线单晶结构分析等证明，随着不同的LiCl/LnCl_3摩尔比和结晶条件的不同，可以得到不同组成的LnCl_3-LiCl-TNF配合物。对(LaCl)(THF)_2(μ_2-Cl)_4[Li(THF)_2]_2和(LaCl)DME(μ_3-Cl)(μ_2-Cl)_5(La·DME)Li(THF)_2晶体的结构分析表明，前者为单斜晶系，P21/C空间群。a=10.542(4), b=32.236(4), c=11.182(6)A °; β=113.50(3) °, V=3484.97 A °~3. Z=4, R=0.0471；后者为三斜晶系，PT空间群，晶胞参数是：a=11.123(3), b=16.564(5), c=8.653(3)A °;α=95.16(3), β=95.63(3), γ=74.71(3) °;V=1527.0A °~3。Z=2，R=0.0303。实验结果还表明，μ_2-和μ_3-氯桥键是LnCl_3-LiCl-THF类配合物中最基本、最重要的配位键，这种键是通过多重键的方式起着稳定分子结构的作用。当进行与有机配体的交换反应时，由于它们的特殊稳定性，能起到阻止轻稀土有机配合物歧化反应的作用。II环戊二烯基轻镧系氯化物的合成及其稳定性的研究对(G_5H_5)_3Ln·THF和LnCl_3·3LiCl-THF (Ln=La, Nd)溶液反应的研究表明，由于μ_2-氯桥键的作用，轻稀土环戊二烯基化合物中环戊二烯基的再分配反应，在0℃或室温下都能迅速进行。通过两者不同的摩尔比反应，经元素分析、红外光谱、~1H NMR和质谱鉴定，方便地合成了C_5H_5 LnCl_2·2LiCl·5THF和(C_5H_5)_2LnCl.LiCl·nTHF (Ln=La, Nd)等配合物。这一结果表明(C_5H_5)_2LnCl.LiCl·nTHF配合物不仅能稳定地存在于THF溶液中，而且能在一定条件下析出结晶。对(C_5H_5)_2LaCl.LiCl·4THF的晶体结构测定表明，该晶体属于正交晶系，Pc2m空间群。a=12.306(4), b=23.056(6), c=26.701(11)A°; V=7575.81A°~3;而(C_5H_5)_2LaCl·LiCl(DME)_2THF晶体则属于六方晶系，a=12.967(4), b=12.967(4), c=24.108(10)A°;V=3510 A°~3。通过(G_5H_5)_3Ln·THF与LnCl_3·3THF (Ln=La, Nd)的反应进一步研究了轻稀土环戊二烯基氯化物的稳定性。经元素分析，红外光谱和晶体结构分析表明合成了[(η~5-C_5H_5)_4La_3Cl_5·3THF]_2·9THF和(C_5H_5)_2 NdCl·THF配合物，前者属于三斜晶系，P1空间群。a=11.690(3), b=11.750(5), c=18.433(6)A°; α=98.75(3), β=95.62(3), γ=118.92(2)°; V=2147.06 A°~3. Z=1, R=0.099。对环戊二烯基轻稀土氯化物的稳定性进行了较详细地讨论。结果表明，THF的用量和化合物的溶解度是影响产物组成的决定因素。当THF的量不足以溶解所生成的产物时，就会歧化成溶解度最大((C_5H_5)_3Ln·THF)和最小(LnCl_3·nTHF)的两种组分。反之，环戊二烯基轻稀土化合物(Ln=La, Nd)中环戊二烯基的再分配反应就能顺利进行。经元素分析和结构测定，在((C_5H_5)_3Nd·THF)和NdCl_3·LiCl-THF溶液的反应体系中，偶然分离得到了[(η~5-C_5H_5)_4Nd_4(μ_4-o)(μ_2-Cl)_8] [Li(DMP)_2THF]_2这一不合常规的化合物，其晶体属于正交晶系，Pna2,空间群a=19.010(7), b=23.231(6), c=14.180(4); V=6261.91 A°~3。Z=4, R=0.054。说明在一定条件下,μ-氧桥键也起到了稳定分子结构的作用。推测了各类环戊二烯基轻稀土氯化物在THF中的合成反应机理,在LiCl存在的反应体系中Ln cl cl Li桥键能与环戊二烯基发生交换反应;在(C_5H_5)_3Ln·THF和LnCl_3·3THF的反应体系中,首先存在着LnCl_3分子之间的互相作用，因而易于形成双核或多核配合物。这类配合物以晶体形式析出时，易于发生结构上的变化，即化合物的结晶形态与溶液中的形态不一定相同。探索了环戊二烯基烯丙基稀土化合物新的合成方法。找到了真空加热脱水制备氯化稀土的最佳条件，其产物纯度在97%以上。通过加入Co_3O_4/Wo_3催化助燃剂的方法，提高了测定稀土有机化合物中碳含量的准确性。

苄基环戊二烯基和茚基稀土二氯化物的合成与结构

本文通过元素分析，红外光谱、水解产物质谱、核磁共振、热失重分析及x-光单晶衍射分析，确认合成了下述两种新型稀土金属有机配合物。并对它们结构特点进行了研究和讨论。(1) ErCl_3 + C_6H_5CH_2C_5H_4Na → (THF) C_6H_5CH_2C_5H_4ErCl_2·3THF + NaCl; (2)GuCl_3·nTHF + C_9H_7K → (THF) C_9H_7GuCl_2·3THF + Kcl; 在第一种配合物的合成中，讨论了苄基环戊二烯与无水氯化稀土反应的条件。并首次成功的合成了苄基环戊二烯基稀土配合物。对于第二种化合物的合成，采取了与文献不同的反应条件及合成方式。提高了产物收率并第一次得到了茚基稀土二氯化物的单晶结构表征。上述两类配合物均对空气、水汽敏感，均可溶于四氢呋喃溶剂中，难以溶解在汽油等烷烃溶剂中。其中C_6H_5CH_2C_5H_4ErCl_2·3THF在DME·Et_2O甲苯等溶剂中也有较为良好的溶解性。在C_6H_5CH_2C_5H_4ErCl_2·3THF的红外光谱中，1600cm~(-1)、1490cm~(-1)和1450cm~(-1)为苯环骨架振动吸收峰，700cm~(-1)为取代苯环的面外弯曲振动吸收峰，2980cm~(-1)，2880cm~(-1)为CH_2的振动吸收峰，1600cm~(-1)、1040cm~(-1)和860cm~(-1)为环戊二烯基的特征吸收峰，1060cm~(-1)、910cm~(-1)为四氢呋喃分子的特征吸收峰，460cm~(-1)为Ln-Cl键的特征吸收峰。其分子结构见图I，晶体为单斜晶系，空间群为P21/n、晶胞参数a = 11.622A. b = 10.281A, c = 26.040A. β = 86.65°、V = 3106.09A、E = 4L。最终端离因子R = 0.050。中心离子Er~(3+)处于八面体中心，配位数为8。化合物C_9H_(17)GdCl_2·3THF的红外光谱中，出现的四氢呋喃分子特征峰为1050cm~(-1), 900cm~(-1)。茚基特征峰为845cm~(-1)和1020cm~(-1)；GuCl键吸收峰为460cm~(-1)，热失重分析表明，配合物分子中含有三个四氢呋喃分子。单晶结构见图II，单晶属单斜晶系，P21空间群，晶胞参数a = 10.468A, b = 11.888A, c = 11.854A, β = 108.46°, D = 1399.3A~3。最后一改性因子R = 0.042。平均键长Gd-C（环）为2.739，Gd-O为2.444A，两个Gd-Cl键长分别为2.583A和2.721A，夹角Cl(1)-Gd-Cl(2)为158.0°。比较所得两个配合物，它们具有相同的化学组成形式，单晶结构也非常相似。在苄基环戊二烯基化合物结构中Cl(1)-Er-Cl(2)夹角为156.3°，而C_9H_7GdCl_2·3THF中相应角度为158.0°，前者较后者小的不到两度，这可能与取代环戊二烯基的空间位阻小大有关。

中国横断山区裂腹鱼亚科(Schizothoracinae)部分类群的系统分类和谱系地理学研究

论文以线粒体细胞色素b 基因对裂腹鱼属鱼类的两个分布广泛的物种 (灰裂腹鱼Schizothorax griseus 和光唇裂腹鱼Schizothorax lissolabiatus)进行了谱系地理学研究；对灰裂腹鱼进行了物种分化研究；对光唇裂腹鱼进行了地理变异研究；并进一步对横断山区分布的裂腹鱼属鱼类进行了谱系地理学研究；整理了中国境内伊洛瓦底江水系分布的裂腹鱼属鱼类。对灰裂腹鱼和光唇裂腹鱼的谱系地理学研究结果表明：1、来自不同水系的灰裂腹鱼和光唇裂腹鱼个体间存在明显的遗传差异，两个物种各自不呈单系；灰裂腹鱼和光唇裂腹鱼同域分布的个体有共享单倍型的情况；北盘江、牛栏江、乌江和元江的个体在系统树上有较近的亲缘关系。2、对灰裂腹鱼进行了重新描述并对来自于不同水系被认为是灰裂腹鱼的标本进行了查看，结果表明：灰裂腹鱼分布于金沙江下游及其支流；分布于澜沧江的，过去被认为是灰裂腹鱼的种类代表裂腹鱼属鱼类一新种——裸腹裂腹鱼Schizothorax nudiventris sp. nov.；分布于南盘江的过去被认为是灰裂腹鱼的种类代表一新种——异鳔裂腹鱼Schizothorax heterophysallidos sp. nov.；分布于北盘江的过去被认为是灰裂腹鱼的种类代表一新种——北盘裂腹鱼Schizothorax beipanensis sp. nov.。3、本研究还陈述了光唇裂腹鱼的各地理种群(怒江、澜沧江、元江、南盘江和北盘江)部分形态特征以及差异情况。主成分分析结果表明：怒江和澜沧江个体在形态上无差异；澜沧江上游和下游个体在部分特征上表现出一定程度上的渐变异。4、横断山区裂腹鱼属鱼类的谱系地理学研究表明：系统树不支持裂腹鱼属鱼类亚属的划分；本属不同种类Cyt b 基因序列的最大遗传距离为11.2%；怒江和澜沧江的个体以较高的支持率聚成一单系；伊洛瓦底江水系与雅鲁藏布江的个体以较高的支持率聚成一单系；金沙江流域与元江、南盘江、北盘江的个体聚成一单系；晚中新世(9.5 Ma) 和早上新世(3.6 Ma)的青藏高原的强烈隆升可能是横断山区裂腹鱼属鱼类物种分化的重要时间；裂腹鱼属鱼类的演化是历史生物地理学过程中隔离分化假说的一个实例；横断山区的古河道向南入海可能有3 个方向，它们是雅鲁藏布-伊洛瓦底江方向、怒江-澜沧江方向、金沙江及其支流-红河方向(包括南盘江-红河)；不支持长江第一湾为袭夺湾的观点，古金沙江入古红河可能不经剑川-洱海一线；滇中、滇东北水系发育复杂。5、本研究还对中国境内伊洛瓦底江水系分布的裂腹鱼属鱼类进行了整理。认为本地区裂腹鱼属鱼类共8 种(包括2 新种)：南方裂腹鱼Schizothorax meridionalis、奇异裂腹鱼Schizothorax heteri sp. nov.、独龙裂腹鱼Schizothorax dulongensis、软刺裂腹鱼Schizothorax malacathus、少鳞裂腹鱼 Schizothorax oligolepis、吸口裂腹鱼Schizothorax myzostomus、细身裂腹鱼 Schizothorax elongatus 和白体裂腹鱼Schizothorax leukus sp. nov.。

SPECTROSCOPIC INVESTIGATION OF HYDROGEN-DOPANT COMPLEXES IN BULK P-TYPE AND IMPLANTED N-TYPE CRYSTALLINE SILICON

Infrared absorption experiments have been performed on hydrogenated and deuterated bulk boron- and aluminum-doped-Si and implanted P, As, and Sb donors in silicon. A first evidence of complex formation in bulk p-type Si is obtained and the spectra confirm the anomalous 3.3-cm-1 deuterium frequency shift with respect to boron isotopes. The ratio of the D-B-11 and D-B-10 peak areas is found to be the same as that of the two boron isotopes natural abundance. In donor-implanted silicon, a quantitative analysis of the obtained data has allowed a rough estimate of the passivating rate due to diffusing deuterium. While the frequencies of the various vibrational lines are found to be in agreement with those reported in the literature, the data on the broad line at 1660 cm-1 (H) or 1220 cm-1 (D) seem to suggest an assignment of this peak to a complex in the bulk involving some type of defect due to the implantation process.

吸水链霉菌、放线菌Sp.253和金色毛壳菌的次生代谢产物研究

链霉菌是十分重要的一类放线菌，绝大多数的抗生素都由该类细菌产生。毛壳属真菌是一类重要的丝状真菌，从中也发现有很多结构新颖、活性独特的活性物质。因此本论文对两株链霉菌的活性成分及一株金毛壳菌的次生代谢产物进行了研究。 1．从吸水链霉菌（Streptomyces hygroscopicus 1.358）液态发酵产物（乙酸乙酯提取物）中分离得到3个化合物，通过波谱方法鉴定为RK955A (1)、Nigericin（2）、Elaiophylin（3）。以青霉素耐药-金黄色葡萄球菌作为指示菌的抗菌活性测定表明，三者均具有较强抗菌活性。 2．通过抗肿瘤体外活性筛选模型筛选得到得到一株链霉属土壤放线菌，从中分离得到六个化合物：苯乙酰胺（4）、苯丙酰胺（5）、肉桂酰胺（6）、3-（N-（甲酰胺基）乙酰基）吲哚（7）、鸟苷磷酸（8）、鸟苷（9）。 3．从金色毛壳菌（Chaetomium aureus）的固态培养物中分离得到13个化合物，利用波谱方法将其鉴定为：金毛壳菌素A（10）、金毛壳菌素B（11）、Eugenetin（12）、Eugenitol（13）、Chaetoquadrin A（14）、Chaetoquadrin B（15）、Chaetoquadrin G（16）、Chaetoquadrin H（17）、Chaetochromin A（18）、Sterigmatocystin（19）、O-methylsterigmatocystin（20）、3β-羟基-麦角甾-5，7，22-三烯（21）和过氧麦角甾醇（22）。 4．综述了聚醚类抗生素的结构、生物合成、生物活性及作用机理。 The genus Streptomyces (Actinomycetes) is an important group of microbe. Most antibiotics known nowdays are discovered from species of Streptomyces. The fungi of the genus Chaetomium have attracted much attention because various kinds of secondary metabolites with diverse bioactivities have been found from them. Thus, the bioactive compounds from two strains of Streptomyces and the secondary metabolites of Chaetomium aureus were investigated. 1. Three compounds were isolated from the ethyl acetate extract of the fermentation broth of Streptomyces hygroscopicus. They are identified to be elaiophylin (1), nigericin (2), and antibiotic RK955A (3) on the basis of their spectroscopic data. Compounds 1-3 possess antibacterial activities against Staphyloccocus aureus. 2. It was found that the extract of the fermented broth of a strain of Actinomycetes could inhibit some tumor cel lines. Separation of the bioactive fraction led to the isolation of six compounds. They were characterized to be phenylacetamide (4), phenylpropylamide (5), trans-cinnamamide (6), 3- (N- (formylmethyl) acetamide) indole (7), guanylicacid (8), and guanosine (9). 3. From the fermented broth of Chaetomium aureus, 13 compounds were isolated for the first time. They were determined to be chaetomiumycin A (10), chaetomiumycin B (11), eugenetin (12), eugenitol (13), chaetoquadrin A (14), chaetoquadrin B (15), chaetoquadrin G (16), chaetoquadrin H (17), chaetochromin A (18), sterigmatocystin (19), O-methylsterigmatocystin (20), 3β-hydroxyergosta-5, 7, 22-triene (21) and peroxy-ergosterol (22). Compounds 10 and 11 are new ones. 4. Structure, biosynthesis, biological activity, and mechanisms of polyether antibiotics were reviewed.

Synthesis, structure and photochromic properties of a novel 1,6-hexanediamine trimolybdate supramolecular compound

A novel supramolecular compound 1,6-hexanediamine trimolybdate ((C6H18N2[Mo3O10], denoted as HDAMo) has been synthesized by a hydrothermal method and its structure has been characterized by elemental analyses, Fourier transform infrared (FT-IR) spectra, single-crystal X-ray diffraction (XRD) technique. This single crystal compound consists of protonated 1,6-hexanediamine (HDA) cations and polyoxometalate [Mo3O10](2-) anions. Its crystal structure belongs to monoclinic system (space group P2(1)/n) with a = 7.7508(14), b = 11.467(2), c = 16.167(3) angstrom, beta = 92.689(3)degrees, V = 143 5.3(5) angstrom(3), Z = 4 and D-ealc = 2.619 g cm(-3). The final statistics based on F-2 are GOF = 0.980, R-1 = 0.0261 and wR(2) = 0.0506 for I > 2 sigma(I). XRD analysis revealed that in the crystal structure of HDAMo, novel infinite [Mo3O10](2-) chains parallel to a axis are made up of distorted MoO6 octahedra connected by corners and edges. The protonated HDA cations occupy channels formed by [Mo(3)O3(10)](2-) Chains and exhibit strong hydrogen bond interactions to terminal and bridging oxo groups of the chains. The [Mo3O10](2-) chains linked through protonated HAD cations formed a one-dimensional network. The HDAMo compound shows novel photochromic properties, i.e., its color changes from white to reddish brown gradually under UV irradiation. XRD, FT-IR, ESR spectra and XPS are used to investigate the photochromic behavior of the compound.

Crystal structures of EtEDTB center dot 1.4C(2)H(5)OH center dot 5H(2)O and H4EtEDTB(ClO4)(4)center dot C2H5OH (EtEDTB=N, N, N ', N '-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine)

The crystal structures of EtEDTB.1.4C(2)H(5)OH.5H(2)O 1 and H4EtEDTB(ClO4)(4).C2H5OH 2 (EtEDTB = N, N,N',N'-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine) have been determined by single-crystal X-ray diffraction method. Compound 1 crystallizes in the space group P(1) over bar with a = 11.489(2), b = 11.866(3), c = 12.002(3) Angstrom, alpha = 97.47(2), beta = 114.564(13), gamma = 114.11(2)degrees, V = 1266.6(5) Angstrom(3), Z = 1, M-r = 847.48, D-c = 1.111 g/cm(3), F(000) = 456 and mu(MoKalpha) = 0.076 mm(-1). A total of 5207 reflections were measured for 1, of which 4323 were independent. The structure of 1 was solved by direct methods and refined by full-matrix least-squares technique to the final R = 0.0706 and wR = 0.1802 for 1318 observed reflections with I > 2sigma(I). In the structure of 1, centrosymmetric EtEDTB molecules are linked by hydrogen bonds through water and ethanol to form 2-dimensional network. Compound 2 crystallizes in the space group C2/c with a = 24.260(5), b = 13.040(3), c = 17.680(4) Angstrom, beta = 97.50(3)degrees, V = 5545.2(2) Angstrom(3), Z = 4, M-r = 1140.80, D-c = 1.366 g/cm(3), F(000) = 2384 and mu(MoKalpha) = 0.289 mm(-1).

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

Three-phase extraction study of Cyanex 923-n-heptane/H2SO4 system

Phase behavior of the extraction system, Cyanex 923-heptane/H2SO4-H2O has been studied. The third phase appeared at different aqueous H2SO4 concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H2SO4 and H2O are extracted into the middle phase. The H2SO4 concentration in the third phase increases with the increasing aqueous acid concentration (C-H2SO4,C-b) while the water content first increases and then reaches a constant value at CH2SO4,(b) = 11.3 mol l(-1). In the region of C-H2SO4,C-b higher than 5.2 mol l(-1), the composition of the middle phase is only related to the equilibrium concentration of H2SO4 in the bottom phase. H2SO4 and H2O are transferred into the middle phase mainly by their coordination with Cyanex 923 when C-H2SO4,C-b is less than 11.3 mol l(-1). When C-H2SO4,C-b is higher than 11.3 mol l(-1), excess H2SO4 is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923.H2SO4 to C923 . H2SO4 . H2O and then to C923 . (H2SO4)(2) . H2O.

Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

Hydrothermal synthesis, crystal structure and properties of [HPDA][H(2)PDA](2)[As-2(III)-AsMo8V4O40]center dot 3H(2)O (PDA = propane diamine)

[NH3CH2CH2CH2NH2][NH3CH2CH2CH2NH3](2)[(As2AsMo8V4O40)-As-III-Mo-V-O-IV].3H(2)O was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data: monoclinic, C2/c, a = 45.375(9) Angstrom, b = 11.774(2) Angstrom, c = 23.438(5) Angstrom, beta = 96.62(3)degrees. X-ray crystallographic study showed that the crystal structure was constructed by bicapped alpha-Keggin fragments [(As2AsMo8V4O40)-As-III-Mo-V-O-IV](5-) polyoxoanion. The title compound had a high catalytic activity for the oxidation of benzaldehyde to benzoic acid using H2O2 as oxidant in a liquid-solid biphase system.

Infrared and MAS NMR spectroscopic studies of Al18B4O33

The IR spectrum and B-11 and Al-27 MAS NMR spectra of Al18B4O33 are presented and discussed in relation to the possible existence of boron atoms substituting for aluminum atoms. The IR spectrum shows that the strong vibrations of the BO3 groups are present in the 1 500 similar to1 200 cm(-1) region, and very weak bands of BO4 units art present in the region from 1 000 to 1 100 cm(-1). B-11 MAS NMR spectrum indicates that the strong signal for BOB units appears in the region from delta +5 to delta +20, and the very weak signal for BO4 units is at about delta -1, while Al-27 MAS NMR spectrum shows five peaks at about delta +62, +42.1, +14, -4.7 and -6.4, originating from AlO4, AlO4, AlO5, AlO6 and AlO6, respectively, These results reveal that there are minor BO4 units in Al18B4O33, indicating that a small amount of B atoms substitute for Al atoms in the 4-fold coordination.

Hydrothermal synthesis and structure of a bi-capped Keggin polyoxoanion, [(As2AsMo8V4O40)-As-III-Mo-V-O-IV](5-)

The title compound, [NH3CH2CH2CH2NH2][NH3CH2CH2CH2NH3](2)[As-2(III) As-v Mo-8 V-4(IV) O-40] (.) 5H(2)O, was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data: monoclinic, C2/c, a = 45.375(9) Angstrom, b = 11.774(2) Angstrom, c = 23.438(5) Angstrom, beta = 96.62(3)degrees. X-ray crystallographic study showed that the crystal structure was constructed by bi-capped alpha -Keggin fragments [(As2AsMo8V4O40)-As-III-Mo-v-O-IV](5-) polyoxoanion. (C) 2001 Elsevier Science B.V. All rights reserved.

16-and 18-electron Cp*Rh complexes with 1,2-dicarba-closo-dodecabofane(12)-1,2-dichalcogenolato ligands, as studied by multinuclear magnetic resonance

The reaction of [Cp*RhCl2](2) 1 with dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-dithiolate (a) and -diselenolate (b) afforded the 16-electron rhodium(III) half-sandwich complexes Cp*Rh[E2C2(B10H10)] [E=S (3a), Se (3b)]. The 18-electron trimethylphosphane rhodium(III) half-sandwiches Cp*Rh(PMe3)[E2C2(B10H10)] 4a-c were prepared from the reaction of Cp*RhCl2(PMe3) 2 with the same dichalcogenolates, including the ditelluride (c). The complexes 4a,b could also be obtained from the reaction of 3a,b with trimethylphosphane. The molecular geometry of 4b was determined by X-ray structural analysis. The 16-electron complexes 3 an monomeric in solution as shown by multinuclear magnetic resonance (H-1-, B-11-, C-13-, P-31- Se-77-, Rh-103-, Te-125-NMR). also in comparison with the data for the trimethylphosphane analogues 4a-c and for 6a in which the rhodium bears the eta(5)-1,3-C5H3 Bu-t(2) ligand. The Rh-103 nuclear shielding is reduced by 831 ppm (3a) and 1114 ppm (3b) with respect to the 18-electron complexes 4a,b. Similarly, the Se-77 nuclear shielding in 3b is reduced by 676.4 ppm with respect to that in 4b. (C) 1999 Elsevier Science S.A. All rights reserved.