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The stabilisation of novel bonding modes in group 2 complexes

第 2 族配合物中新型键合模式的稳定性

基本信息

批准号：
EP/G011850/1
负责人：
Deborah Kays
金额：
$ 40.1万
依托单位：
University of Nottingham
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2009
资助国家：
英国
起止时间：
2009 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FG011850%2F1
关键词：
stabilisation novel bonding modes group

项目摘要

The proposed research seeks to prepare compounds featuring unprecedented bonding modes of the alkaline earth metals and substantially expand the very limited known range of such systems. The recent report of the first complex to feature a bond between two magnesium centres, in which the Mg atoms possess an oxidation state of +1, highlights a number of important questions such as whether the other alkaline earth elements can display analogous bonding modes. This proposal aims to synthesise such compounds featuring the other alkaline earth elements, e.g. the first examples of (beryllium-beryllium)2+ and (calcium-calcium)2+ units. Theorists have proposed these systems to be stable. This chemistry will also be extended towards the synthesis of novel complexes where the beryllium and calcium atoms are bonded to transition metals. The study of main group and transition metal compounds featuring low-coordinate centres and element-element bonds is of great importance, both from the investigation of the fundamental structure and bonding within these systems which challenge our accepted ideas of bonding and from the potential of these highly reactive centres to act as reaction catalysts.Information regarding the bonding within these metal-metal bonded species will come from structural, spectroscopic and theoretical calculations, together with an examination of the fundamental patterns of reactivity displayed by these compounds towards a range of small molecules; including, for example polar/non polar bonds, multiple bonds, diatomics and triatomics, allowing us to develop new reaction pathways such as insertion and cycloaddition-type chemistries. We will also investigate the use of these metal-metal bonded systems as precursors towards new metal-rich cluster compounds via controlled decomposition reactions. The high reactivity of these alkaline earth compounds, although posing practical challenges, makes them not only fascinating from both the fundamental study of their bonding, but also due to their potential application in small molecule activation and catalytic chemistry. Therefore, the results gained from this study will be of great benefit to the scientific community, both from this fundamental structure and bonding viewpoint and the eventual exploitation of their high reactivity in organic reactions and small molecule activation. Additionally, the use of Mg and Ca-based catalysts for these organic reactions would be cheaper and more environmentally benign than many of the lanthanide and transition metal systems currently being exploited for this purpose. The development of metal-rich cluster compounds, stabilised and solubilised by organic chemical groups, are potentially useful in the modelling of solid hydrogen storage materials using solution techniques, which may lead to increased understanding and therefore improvement and optimisation of these compounds.The stabilisation and study of such systems will challenge our accepted ideas of bonding for these elements. Investigation of the bonding within compounds such as these is essential as it contributes towards our understanding of the fundamental structure and bonding within the alkaline earth elements, it is therefore a highly desirable area of research for inorganic chemists and should be actively pursued. We therefore seek EPSRC funding for a 3 year PDRA at Nottingham, technician support, consumables, modest equipment costs associated with the setting up of an independent research laboratory and travel costs for conference attendance. This synthetically challenging research programme will benefit greatly from full participation by DLK, who, as a new lecturer, has a reduced teaching load.

拟议的研究旨在制备具有前所未有的碱土金属键合模式的化合物，并大大扩展此类系统的非常有限的已知范围。最近报道的第一个复合物具有两个镁中心之间的键，其中镁原子具有+1的氧化态，突出了一些重要的问题，如其他碱土元素是否可以显示类似的键合模式。该提案旨在合成具有其他碱土元素的此类化合物，例如（铍-铍）2+和（钙-钙）2+单元的第一个实例。理论家认为这些系统是稳定的。这种化学也将扩展到合成铍和钙原子与过渡金属键合的新型络合物。具有低配位中心和元素-元素键的主族和过渡金属化合物的研究是非常重要的，无论是从对这些系统中的基本结构和键合的研究，挑战我们所接受的键合思想，还是从这些高活性中心作为反应催化剂的潜力，关于这些金属-金属键合物种中的键合的信息将来自结构，光谱和理论计算，以及这些化合物对一系列小分子显示的反应性的基本模式的检查;包括，例如极性/非极性键，多重键，双原子和三原子，使我们能够开发新的反应途径，如插入和环加成型化学。我们还将研究使用这些金属-金属键合系统作为前体，通过受控的分解反应，形成新的富金属簇合物。这些碱土金属化合物的高反应性，虽然提出了实际的挑战，使他们不仅从他们的键合的基础研究，而且由于他们在小分子活化和催化化学的潜在应用令人着迷。因此，从这项研究中获得的结果将对科学界非常有益，无论是从这种基本结构和键合的观点，还是最终利用它们在有机反应和小分子活化中的高反应性。此外，将Mg和Ca基催化剂用于这些有机反应将比目前为此目的开发的许多镧系元素和过渡金属体系更便宜且更环保。富金属原子簇化合物的发展，稳定和溶解的有机化学基团，是潜在的有用的固体储氢材料的模拟使用溶液技术，这可能会导致增加理解，因此，改善和优化这些化合物。这种系统的稳定和研究将挑战我们接受的想法，这些元素的键合。研究这些化合物中的键合是必不可少的，因为它有助于我们理解碱土元素的基本结构和键合，因此它是无机化学家非常希望的研究领域，应该积极追求。因此，我们寻求EPSRC资助诺丁汉的3年PDRA、技术人员支持、消耗品、与建立独立研究实验室相关的适度设备成本和出席会议的差旅费。这个综合性的具有挑战性的研究计划将大大受益于DLK的全面参与，作为一名新讲师，他的教学负担减轻了。