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Mapping the chemistry of phosphorus-containing analogues of urea. From fundamental chemistry to high-performance compounds and materials.

绘制尿素含磷类似物的化学图谱。

基本信息

批准号：
EP/M027732/1
负责人：
Jose Goicoechea
金额：
$ 46.45万
依托单位：
University of Oxford
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2015
资助国家：
英国
起止时间：
2015 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FM027732%2F1
关键词：
Mapping chemistry phosphorus containing analogues

项目摘要

The isolobal analogy is frequently invoked to draw comparisons between the fundamental chemistry of small inorganic molecules and more established organic species. For example, the diagonal relationship between a methine fragment (C-H) and phosphorous has led to the latter being nicknamed a "carbon-copy". This has resulted in extensive chemistry aimed at developing phosphorus-containing analogues of organic molecules such as phospha-alkenes (RP=PR) and -alkynes (PCR), amongst many other examples. However, an isolobal relationship does not imply that phosphorus-containing congeners of specific organic molecules can be readily synthesized. In fact, the synthesis of relatively simple molecules where a C-H unit, or even an isoelectronic element such as nitrogen, has been replaced by a phosphorus atom still represents a significant technical and intellectual challenge. In this regard synthetic inorganic chemistry lags far behind organic synthesis.As a case in point, while urea was first synthetically isolated in 1829, it was not until late 2013 that our research group succeeded in the isolation of a phosphorus analogue, phosphinecarboxamide. Considering the importance of urea as a chemical feedstock, we propose to utilize this heavier analogue (and other related species) for the synthesis of novel molecules and solids. This is a completely new approach to organophosphorus compounds which, while inherently risky, has the potential to generate fascinating new species that are related to those derived from urea, but that have fundamentally different chemical and physical properties. Current methods for the synthesis of phosphorus-containing chemicals (employed, for example, in pharmaceuticals and specialty chemicals such as photo-initiators) require the use of phosphorus (III) chloride as a feedstock. While such processes currently represent the industrial state-of-the-art, the use of alternative non-toxic precursors remains a highly desirable objective. Alternative strategies to organophosphorus compounds based on the chemical activation of white phosphorus are possible (and well-documented in the literature), however such transformations are often marred by low selectivities or require multiple subsequent manipulations to be competitive with industrial processes. Moreover, white phosphorus is itself highly pyrophoric and dangerous to manipulate. The risks associated with these precursors make the identification of novel phosphorus-atom feedstocks highly desirable.We propose to develop the chemistry of a new class of phosphorus-containing small molecules that are accessible using red phosphorus, a non-pyrophoric allotrope of the element. Ultimately, this will allow us to reduce the safety risks typically encountered when manipulating conventional precursors for the synthesis of specialty chemicals. Building on recent breakthroughs in our laboratory, we will explore the chemistry of the 2-phosphaethynolate anion and phosphinecarboxamide, two novel phosphorus-containing analogues of otherwise ubiquitous chemicals (the cyanate ion and urea, respectively). Our ultimate goal is to access novel molecular, supramolecular and polymeric species with potential applications in catalysis, chemical sensing and materials chemistry. This proposal represents an entirely novel approach to the development of phosphorus-containing molecules and solids of enormous potential societal and economic impact.

等瓣线类比经常被用来比较无机小分子的基本化学性质和更成熟的有机物种。例如，次甲基片段（C-H）和磷之间的对角关系导致后者被昵称为“碳拷贝”。这导致了广泛的化学，旨在开发有机分子的含磷类似物，如磷-烯烃（RP=PR）和-炔（PCR），以及许多其他例子。然而，等瓣关系并不意味着特定有机分子的含磷同系物可以容易地合成。事实上，合成相对简单的分子，其中C-H单元，甚至是氮等电子元素，已经被磷原子取代，仍然代表着一个重大的技术和智力挑战。在这方面，合成无机化学远远落后于有机合成。作为一个恰当的例子，虽然尿素在1829年首次合成分离，但直到2013年底，我们的研究小组才成功分离出磷类似物膦酰胺。考虑到尿素作为化学原料的重要性，我们建议利用这种较重的类似物（和其他相关物种）合成新的分子和固体。这是一种全新的有机磷化合物方法，虽然固有风险，但有可能产生与尿素衍生物相关的迷人的新物种，但具有根本不同的化学和物理性质。目前用于合成含磷化学品的方法（例如，用于药物和特种化学品如光引发剂中）需要使用氯化磷（III）作为原料。虽然这些方法目前代表了工业上的最新技术水平，但是使用替代的无毒前体仍然是非常理想的目标。基于白色磷的化学活化的有机磷化合物的替代策略是可能的（并且在文献中有充分的记载），然而这种转化通常被低选择性破坏或者需要多次后续操作以与工业方法竞争。此外，白色磷本身具有高度自燃性，操作起来很危险。与这些前体相关的风险使得识别新的磷原子feedstocks非常可取的。我们建议开发一类新的含磷小分子的化学，这些含磷小分子可以使用赤磷，一种非自燃的元素的同素异形体。最终，这将使我们能够减少在操作用于合成特种化学品的常规前体时通常遇到的安全风险。在我们实验室最近取得的突破的基础上，我们将探索2-磷酸乙炔阴离子和膦酰胺的化学性质，这两种新型的含磷类似物是普遍存在的化学物质（分别是氰酸根离子和尿素）。我们的最终目标是获得新的分子，超分子和聚合物物种在催化，化学传感和材料化学的潜在应用。该提案代表了开发具有巨大潜在社会和经济影响的含磷分子和固体的全新方法。

项目成果

期刊论文数量（9）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Phosphinecarboxamide as an unexpected phosphorus precursor in the chemical vapour deposition of zinc phosphide thin films.

DOI：
10.1039/c8dt00544c
发表时间：
2018-07
期刊：
Dalton transactions
影响因子：
4
作者：
Samuel V F Beddoe;Samuel D. Cosham;A. Kulak;A. Jupp;J. Goicoechea;G. Hyett
通讯作者：
Samuel V F Beddoe;Samuel D. Cosham;A. Kulak;A. Jupp;J. Goicoechea;G. Hyett

The Aluminyl Anion: A New Generation of Aluminium Nucleophile

铝基阴离子：新一代铝亲核试剂