Synthetic Phosphorus Chemistry: The Systematic Development of Organophosphorus Molecules and Polymers

本研究旨在系统地发展磷及其化合物的化学。磷是一种重要的元素，不仅是生命所必需的，而且被用于大量的商业产品。我们工作的主要目标是开发含有磷作为主链关键成分的聚合物。特定聚合物的性质和潜在应用是构成链结构的原子的排列和类型的直接结果。今天使用的大多数聚合物都是由含有碳、氧和/或氮原子的链组成的，这些原子具有明确的序列。由其他元素组成的聚合物的发展还处于起步阶段，然而，由于它们独特的物理性质和化学功能，这些所谓的无机聚合物有很大的前景。例如，由硅和氧原子交替组成的商用聚合物有机硅具有极高的灵活性和温度稳定性，这是有机聚合物无法达到的。无机聚合物开发的关键挑战是缺乏将无机元素加入到长链中的一般合成路线。 烯烃的C=C键的加成聚合可能是工业聚合物生产中最重要的方法，用于制造聚乙烯、聚丙烯、聚苯乙烯、丙烯和特氟龙，仅举几例。长期以来，人们一直认为含杂原子的多键不适合加成聚合方法。我们已经证明了磷杂烯中P=C键的加成聚合是合成含磷聚合物的一条途径。这是一个将在未来五年内严格探讨的问题。这一新的聚合反应的机理仍然存在疑问，并在此概述了我们的研究方向。我们还将探索手性磷杂烯的合成，这些手性磷烯可以直接用作过渡金属催化和小分子活化的配体，或者作为单体提供用于聚合物负载催化的聚合物配体。在最后一个追求领域，我们建议开发新型的p-共轭含磷聚合物，利用磷的化学功能作为一种手段来定制电子性质，以应用于小分子传感器材料等领域。 最后，本文提出的工作进一步扩展了磷的迷人化学。这项工作将增加无机化学和聚合物科学的基础知识，并将为未来的技术应用提供基础。

The research proposed herein aims to systematically develop the chemistry of phosphorus and its compounds. Phosphorus is an important element, not only being essential for life but being used in a wealth of commercial products. The primary objective of our work is to develop polymers that contain phosphorus as a key component of the main chain. The properties and potential applications of a particular polymer are a direct consequence of the arrangement and type of atoms that make up the chain structure. Most polymers in use today are comprised of chains containing carbon, oxygen, and/or nitrogen atoms in well-defined sequences. The development of polymers composed of other elements is at its infancy, however, there is considerable promise for these so-called inorganic polymers due to their unique physical properties and chemical functionality. For example, the commercial polymer silicone, consisting of alternating silicon and oxygen atoms, has extreme flexibility and temperature stability that is unattainable with organic polymers. The key challenge to inorganic polymer development is the lack of general synthetic routes to incorporate inorganic elements into long chains. The addition polymerization of the C=C bond of olefins is perhaps the most important method of industrial polymer production being used to make polyethylene, polypropylene polystyrene, acrylics, and Teflon, to name a few. It was long believed that heteroatom-containing multiple bonds were not suited for addition polymerization methods. We have shown that the addition polymerization of the P=C bond in a phosphaalkene is a route to phosphorus-containing polymers. This is a subject that will be rigorously pursued during the next five years. The mechanism of this new polymerization reaction is still in question and our proposed investigations are outlined herein. We will also explore the synthesis of chiral phosphaalkenes that may be employed directly as ligands for transition metal-catalysis and small-molecule activation or as monomers to afford polymeric ligands for use in polymer-supported catalysis. In a final area of pursuit, we propose to develop new types of p-conjugated phosphorus-containing polymers that exploit the chemical functionality of phosphorus as a means to tailor the electronic properties for application in areas such as small molecule sensor materials. In closing, the work proposed herein further expands the fascinating chemistry of phosphorus. This work will lead to gains in fundamental knowledge of inorganic chemistry and polymer science, and will provide a foundation for future technological applications.