Synthetic, Mechanistic, and Catalytic f-Element Organometallic Chemistry

西北大学化学系Tobin J. Marks博士是 由无机，生物无机和有机物计划支持， 化学部的有机金属化学的研究 f-元素（锕系元素和镧系元素），与早期密切相关 过渡金属该项目的目标是设计，表征， 从结构、机械和热力学的角度来理解 涉及F元素的新的化学计量和催化转化 有机金属分子该项目由四个紧密 互连组件：（1）滴定量热法将用于 量化金属配位体多重键的强度， “零价”f元素络合物，含有重基的键 14-16个配体，并牢固地“锚定”现有的键能数据，并牢固地“锚定”现有的键能数据 （2）绝对规模的汇编;（3）绝对规模的范围和机制 有机镧系元素/有机锕系元素催化的反应，其中元素H 将确定添加到不饱和碳-碳键上的键， 重点集中在热力学上可行的加氢胺化， 氢化膦化、硼氢化和硫醇化反应;（3） 具有C1的手性镧系元素和锕系元素络合物的性质 对称连接将在结构方面进行研究， 立体化学完整性和在对映选择性催化中的功效 （2）中描述的类型的变换;和（4） 有机镧系元素催化的链转移反应， 聚合与元素-H/金属-C转位过程耦合 将用于生产一系列杂原子“封端”聚烯烃， 和不常见的聚烯烃，其中亚甲基单元直接附加到 聚合物主链。 涉及有机金属化合物的转化是中心的 对美国工业化学的许多领域具有重要意义，包括 用于生产燃料，聚合物材料， 药品和其他经济上重要的化学品。事态发展 在这一领域的发展是至关重要的， 选择性、环境友好和经济上有竞争力的过程 技术.该项目的重点是镧系元素和锕系元素。的 这些元素的有机金属化学直到最近才被 相对未开发，并且对其应用的兴趣越来越大 在聚合催化和有机合成中。这个目标 项目是影响，表征，并了解不寻常的， 涉及f-元素有机金属的潜在有用的变换 分子。

Dr. Tobin J. Marks, Department of Chemistry, Northwestern University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for a study of the organometallic chemistry of the f-elements (actinides and lanthanides), and closely related early transition metals. The goal of the project is to design, characterize, and understand from a structural, mechanistic, and thermodynamic sense novel stoichiometric and catalytic transformations involving f-element organometallic molecules. The project consists of four closely interconnected components:(1) Titration calorimetry will be utilized to quantify the strengths of metal-ligand multiple bonds, of bonds involving `zero-valent` f-element complexes, of bonds involving heavier groups 14-16 ligands, and to firmly `anchor` existing bond energy data compilations on an absolute scale; (2) The scope and mechanism of organolanthanide/organoactinide-catalyzed reactions in which element-H bonds are added to unsaturated carbon-carbon bonds will be determined, with focus being concentrated on thermodynamic feasible hydroamination, hydrophosphination, hydroboration, and hydrothiolation reactions; (3) The properties of chiral lanthanide and actinide complexes having C1 symmetric ligation will be investigated with respect to structure, stereochemical integrity, and efficacy in enantioselective catalytic transformations of the types described in (2); and (4) organolanthanide-catalyzed chain transfer reactions in which olefin polymerization is coupled to element-H/metal-C transposition processes will utilized to produce a series of heteroatom `end-capped` polyolefins, and unusual polyolefins in which methylene units are directly appended to polymer backbones. Transformations involving organometallic compounds are of central importance to numerous areas of U.S. industrial chemistry, including catalytic processes for the production of fuels, polymeric materials, pharmaceuticals, and other economically important chemicals. Developments in this area are crucial to the development of ever more efficient, selective, environmentally benign, and economically competitive process technologies. This project focuses on the lanthanides and actinides. The organometallic chemistry of these elements has until recently been relatively unexplored, and there is growing interest in their application in polymerization catalysis and organic synthesis. The goal of this project is to effect, characterize, and understand unusual and potentially useful transformations involving f-element organometallic molecules.