Opening up New Oxidation States in Metallocene Chemistry Across the Periodic Table

茂金属是夹在两个五元碳环之间的金属原子的化合物，最典型的例子是二茂铁[Fe(C5H5)2]。65年前，二茂铁的发现导致了1973年诺贝尔化学奖的颁发，并引发了一场塑造了当代科学的化学革命。尽管二茂铁及其衍生物普遍存在+2和+3氧化态，但分离的第一排过渡金属的+1氧化态配合物已被证明是难以获得的。茂金属化合物是一类重要的分子，已在不同的研究领域和工业应用中得到应用。我们预计，茂金属阴离子的定向合成和研究将产生重要的新教材数据，并为未来的探索开辟无数前景。在这个项目中，学生将首先使用厌氧合成化学技术来分离第一排过渡金属的衍生茂金属阴离子，其中金属正式处于+1氧化态。我们将研究这些化合物的反应性分布，并将使用大量的光谱技术、磁性测量和高级从头计算来询问它们的电子结构。我们将使用这些数据来通知这个项目的扩展，这样学生就可以合成和研究整个元素周期表中金属的茂金属阴离子。这些结果将为茂金属家族的结构和成键的基本原理提供新的见解，这是它们广泛应用的基础。该项目专注于合成配位化学EPSRC研究领域，学生对化合物的分析与其他EPSRC研究领域相关，包括化学结构和计算和理论化学。

Metallocenes are compounds that contain a metal atom sandwiched between two five-membered carbon rings, and are best exemplified by ferrocene, [Fe(C5H5)2]. The discovery of ferrocene over 65 years ago led to the award of the 1973 Nobel Prize in Chemistry and sparked a chemical revolution that has shaped contemporary science. Although the +2 and +3 oxidation states are ubiquitous for ferrocene and its derivatives, isolated +1 oxidation state complexes of the first row transition metals have proved difficult to access. The metallocene family of compounds are keystone molecules that have found application in diverse research areas and industrial applications. We anticipate that the targeted synthesis and study of metallocene anions will generate important new textbook data and open up numerous vistas for future exploration.In this project, the student will first use anaerobic synthetic chemistry techniques to target the isolation of derivatised metallocene anions of the first row transition metals, where the metal is formally in the +1 oxidation state. We will investigate the reactivity profiles of these compounds, and we will interrogate their electronic structures with a plethora of spectroscopic techniques, magnetic measurements and high-level ab initio calculations. We will use these data to inform the expansion of this project so that the student can synthesise and study metallocene anions for metals across the Periodic Table. The results will provide new insights into the fundamentals of structure and bonding of the metallocene family, which underpin their versatile applications.The project is focused in the synthetic coordination chemistry EPSRC research area, and analysis of the compounds made by the student is of relevance to other EPSRC research areas including chemical structure and computational and theoretical chemistry.