The stabilisation of novel bonding modes in group 2 complexes

提出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，并大大扩展这种系统非常有限的已知范围。最近报道的第一个以两个镁中心之间的键为特征的配合物，其中Mg原子具有+1的氧化态，突出了许多重要的问题，例如其他碱土元素是否可以显示类似的键模式。本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+单位的第一个例子。理论学家提出这些系统是稳定的。这种化学也将扩展到合成新的配合物，其中铍和钙原子与过渡金属结合。对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非常重要，无论是从对这些系统的基本结构和键合的研究，还是从这些高活性中心作为反应催化剂的潜力来看，都挑战了我们公认的键合观念。关于这些金属-金属键的信息将来自结构、光谱和理论计算，以及对这些化合物对一系列小分子的反应性的基本模式的检查；例如，包括极性/非极性键，多键，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。我们还将研究利用这些金属-金属键系统作为前体，通过控制分解反应生成新的富金属簇化合物。这些碱土化合物的高反应活性，虽然带来了实际的挑战，但不仅从它们的键的基础研究，而且由于它们在小分子活化和催化化学方面的潜在应用，使它们具有吸引力。因此，从这个基本结构和键的角度来看，从这项研究中获得的结果将对科学界有很大的好处，并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，在这些有机反应中使用镁和钙基催化剂将比目前为此目的开发的许多镧系元素和过渡金属系统更便宜，更环保。富金属簇化合物的发展，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建模使用溶液技术，这可能会导致增加的理解，从而改进和优化这些化合物。这种系统的稳定性和研究将挑战我们对这些元素结合的公认观念。研究这些化合物中的键是必不可少的，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理想的研究领域，应该积极追求。因此，我们寻求EPSRC资助在诺丁汉进行为期3年的PDRA，技术支持，消耗品，与建立独立研究实验室相关的适度设备成本以及出席会议的差旅费。这个具有综合挑战性的研究项目将从DLK的全面参与中受益匪浅，作为一名新讲师，他的教学负担减轻了。

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.