Si-O Elimination for the Generation of Heteronuclear Metal-Metal Bonds

在过去的四十年里，含有金属-金属键的化合物引起了人们的广泛兴趣。这些化合物令人着迷，并具有潜在的用途，因为它们能够与许多对可持续发展和能源技术(即氢气、二氧化碳)等领域具有重要意义的小分子反应。目前获得金属-金属键的方法使用了危险的碱金属试剂，并且不选择性地排除了异核金属-金属键的进入。本研究将寻求通过消除强的Si-O键来合理地合成含有迄今未见的金属-金属键的主族和过渡金属物种。最初的工作将集中在利用已知的主族金属醇氧化物通过Sigma键易位生成新型主族硅基化合物。随着生成的硅烷库的反应性，尤其是与主基和过渡金属醇盐的反应，将被研究。随着一种经过验证的通过Si-O消除来获得异核金属-金属键的方法，该方法将被应用于更广泛的金属和替代配体系统，以获得含有金属-金属键的低配位物种。

Compounds containing metal-metal bonds have attracted extensive interest over the last four decades. These compounds are fascinating and potentially useful owing to their ability to react with numerous small molecules of significance to areas such as sustainability and energy technologies (i.e. hydrogen, carbon dioxide). Current methods to access metal-metal bonds apply dangerous alkali metal reagents and are unselective precluding access to heteronuclear metal-metal bonds.This research will seek to rationally synthesise Main Group and Transition Metal species containing hitherto unprecedented metal-metal bonding via the elimination of strong Si-O bonds.Initially the work will focus on the generation of novel Main Group silyl compounds generated by sigma-bond metathesis applying known Main Group metal alkoxides. With a library of silyls generated their reactivity, most notably with Main Group and Transition Metal alkoxides, will be investigated.With a validated methodology to access heteronuclear metal-metal bonds via Si-O elimination in hand, this method will be applied to a much wider range of metals and to alternative ligand systems to access low-coordinate species containing metal-metal bonds.