Early transition metal and lanthanide amidate complexes: modular, easily accessed complexes for catalysis

早期的过渡金属，如钛和锆，以及镧系金属已经成功地用于金属介导的有机合成。 作为催化剂，这些金属能够促进通常不能发生的反应。 催化对于工业应用非常重要，因为它以具有成本效益和能源效率的方式促进化学转化，同时最大限度地减少化学废物。 当然，催化是发展环境友好的绿色化学和可持续的化学生产方法的关键。 早期过渡金属和镧系金属对于大规模应用特别有吸引力，因为它们具有低成本和低毒性。 我们研究小组开发的易于制备，廉价的催化络合物显示出在制药，聚合物和精细化工行业中广泛的重要催化转化的前景。 使用上述金属类，我们已经开发了一系列的配合物（酰胺化物配合物），显示出前所未有的和非常理想的催化活性，在选择性的C-N键形成的分子内反应（两个反应伙伴都包含在一个起始材料）。 我们建议继续探索这些络合物的C-N键形成，以实现化学合成中的一个长期目标，即以分子间的方式将胺（N-H键）加成到简单的烯烃（C=C键）上（反应性伴侣是两个独立的分子）。 除了选择性C-N键的形成，我们将探索这种新的络合物家族在C-C偶联反应以及聚合反应中的潜在应用。 最近的研究结果显示，这些配合物在催化制备可生物降解、可堆肥的聚合物方面是有用的。所申请的拨款将支持我们不断努力，全面探索和开发这些新的催化系统。

Early transition metals, such as titanium and zirconium, and lanthanide metals have been used successfully for metal-mediated organic synthesis.  As catalysts, these metals are able to promote reactions that normally cannot occur.  Catalysis is very important for industrial applications, as it promotes chemical tranformations in a cost effective, energy efficient manner while minimizing chemical waste.  Certainly catalysis is key to the development of environmentally friendly green chemistry and sustainable methods for chemical production.  Early transition and lanthanide metals are particularly attractive for large scale applications, due to the fact that they are of low cost and low toxicity.  The easily prepared, inexpensive catalytic complexes developed in our research group show promise for a broad range of important catalytic transformations in the pharmaceutical, polymer and fine chemical industries.  Using the class of metals presented above, we have developed a family of complexes (amidate complexes) that display unprecedented and highly desirable catalytic activity in selective C-N bond formation for intramolecular reactions (both reactive partners are contained in one starting material).  We propose to continue our exploration of these complexes for C-N bond formation, to achieve a long-standing goal in chemical synthesis, the addition of amines (N-H bonds) to simple alkenes (C=C bonds) in an intermolecular fashion (reactive partners are two separate molecules).    In addition to selective C-N bond formation we will be exploring the potential application of this new family of complexes in C-C coupling reactions, as well as polymerization reactions.  Recent results demonstrate the usefulness of these complexes in the catalytic preparation of biodegradable, compostable polymers.The funds requested will support our on-going efforts to fully explore and develop these new catalytic systems.