Synthetic, Mechanistic, and Catalytic f-Element Organometallic Chemistry

无机，生物无机和有机化学计划的这一奖项支持西北大学Tobin J. Marks博士的研究，以研究涉及镧系元素和相关早期过渡金属的新催化转化的基本方面。 将量化有机金属/催化过程中形成和断裂的键的强度。 反应量热法将用于量化金属-配体多重键、金属-主基配体单键的强度，并在绝对尺度上“锚”数据。 这些基本的科学信息将用于：阐明键合，合理化已知的反应模式，并为新的，有用的催化过程的发明开发原则。 新的催化机制将被调查有关的转换，其中元素-H键被添加到不饱和的碳-碳键（氢元素化），以选择性地创建含杂原子的有机分子。 主要重点是选择性C-N，C-P，C-B和C-S键形成过程，研究一系列前体结构（C=C，C=C=C，C=C-C=C），表征速率，选择性，取代基效应，并比较分子内与分子间过程。催化级联，其中偶联键形成过程的受控序列（例如，C-N + C-C）发生在单一和邻近的金属中心也将被研究和完善，作为有用的精细化学品和生物活性分子的最终路线，以及建立新的催化原理。 将研究有机镧系元素催化的聚合方法，其涉及与元素-H/金属-C交换过程或与产生用杂原子“封端”的新型聚合物链（例如，Si、Sn、B、Al）。具有各种对称性环境的手性络合物的性质将在催化转化的对映选择性变体的结构、稳定性和功效方面进行研究。 不寻常的螯合配位体结构具有硫和磷供体原子也将进行研究。此外，还将研究锕系元素配合物，以比较/对比电子结构对催化性能的影响。该项目侧重于有机金属/催化/材料化学，以影响、表征、理解和向社区传播不寻常的和潜在有用的新化学计量和催化反应性原理，这些原理适用于制造更有效、原子经济的催化过程，用于燃料、塑料、药品和其他经济上重要的化学品。 在这个多方面/多学科项目的参与，包括与工业科学家的互动，将准备研究生，本科生和博士后学生，具有不同的背景，在工业，政府实验室和工业生产的职业生涯。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. Tobin J. Marks at Northwestern University to investigate fundamental aspects of new catalytic transformations involving lanthanide and related early transition metals. The strengths of bonds being made and broken in organometallic/catalytic processes will be quantified. Reaction calorimetry will be used to quantify the strengths of metal-ligand multiple bonds, of metal-main group ligand single bonds, and to "anchor" the data on an absolute scale. This fundamental scientific information will then used to: elucidate bonding, rationalize known reaction patterns, and develop principles for the invention of new, useful catalytic processes. New catalytic mechanisms will be investigated pertaining to transformations in which element-H bonds are added to unsaturated carbon-carbon bonds (hydroelementation) to selectively create heteroatom- containing organic molecules. The primary focus is on selective C-N, C-P, C-B, and C-S bond-forming processes, studying a range of precursor structures (C=C, C=C=C, C=C-C=C), characterizing rates, selectivities, substituent effects, and comparing intramolecular vs. intermolecular processes. Catalytic cascades in which controlled sequences of coupled bond-forming processes (e.g., C-N + C-C) take place at single and proximate metal centers will also be studied and refined as ultimate routes to useful fine chemicals and bio-active molecules, as well as to establish new catalytic principles. Organolanthanide-catalyzed polymerization processes will be investigated that involve single or closely poised multiple metal centers coupled to element-H/metal-C exchange processes or to hydroelementation processes that produce new types of polymer chains "end-capped" with a heteroatom (e.g., Si, Sn, B, Al). The properties of chiral complexes having various symmetry environments will be studied with respect to structure, stability, and efficacy in enantioselective variants of catalytic transformations. Unusual chelating ligand structures having sulfur and phosphorus donor atoms will also be studied. In addition, actinide complexes will be investigated to compare/contrast electronic structure effects on catalytic properties.This project focuses on organometallic/catalytic/materials chemistry in order to effect, characterize, understand, and disseminate to the community, unusual and potentially useful new stoichiometric and catalytic reactivity principles applicable to making more efficient, atom- economical catalytic processes for the production of fuels, plastics, pharmaceuticals, and other economically important chemicals. Participation in this multifaceted/multidisciplinary project, including interactions with industrial scientists, will prepare graduate, undergraduate, and postdoctoral students, having diverse backgrounds, for productive careers in industry, government laboratories, and academe.