Carbon-rich Ligands: An approach using hydroruthenation chemistry

具有全碳(Cx)或富碳(CxHy，x&gt；y)配体的络合物的化学是当代有机金属领域的一个巨大兴趣的来源。到目前为止，这些研究的绝大多数都是关于线性多碳配体和线性多烯二基配体(CH)n。虽然许多这些研究都是为了建立可行的合成路线来合成这些不寻常的金属稳定的有机片段，并确定它们的分子和电子结构，但也有许多关于这类材料的潜在应用的热烈讨论。最近，通过支化共轭配体连接金属中心的超支化和树枝状金属有机配合物由于其光学、磁学和催化性能而开始引起人们的关注。这些体系中的绝大多数都具有来自1，3，5-三取代苯核和金属乙炔的支链配体，考虑到人们对富碳有机金属络合物和有机金属超支化体系的兴趣，具有支化全碳或富碳配体的有机金属络合物并不常见，这是相当令人惊讶的。我们建议将希尔教授在炔烃水合作用方面的经验与刘特佐博士对交叉共轭炔烃和富碳配体化学的知识相结合，开发一条合成具有支化富碳配体的有机金属络合物的新途径。为了发展这一计划，我们提议利用EPSRC的海外旅行补助金条款，允许刘特佐博士访问希尔教授的实验室澳大利亚国立大学化学研究学院。在皇家莎士比亚剧团期间，PJL将获得希尔在他的许多优雅研究中使用的氢化化学的第一手经验。预计在这次相对较短的(3个月)访问结束时，基于对这一新的化学领域的探索的新的低山合作将得到很好的建立。

The chemistry of complexes featuring all-carbon (Cx) or carbon-rich (CxHy, x>y) ligands is a source of immense contemporary interest in the organometallic community. To date the great majority of these studies have been concerned with linear polycarbon ligands and the linear polyenediyl ligands (CH)n. While many of these studies are directed towards establishing viable synthetic routes to these unusual metal stablised organic fragments, and in determining their molecular and electronic structures, there are also many enthusiastic discussions of the potential applications of such materials.More recently hyperbranched and dendritic organometallic complexes with metal centres linked by branched conjugated ligands have begun to attract attention as a consequence of their optical, magnetic and catalytic properties. The vast majority of these systems feature branched ligands derived from 1,3,5-trisubsituted benzene cores, and metal acetylide, vinylidene or vinyl based linkages.Given this interest in both carbon-rich organometallic complexes and organometallic hyper-branched systems it is rather surprising that organometallic complexes featuring branched all-carbon or carbon-rich ligands are less common.We propose to combine Professor Hill's experience in alkyne hydrometallation with Dr Low's knowledge of cross-conjugated alkynes and carbon-rich ligand chemistry to develop a new synthetic pathway to organometallic complexes featuring branched carbon-rich ligands.In order to develop this programme we propose to utilise the EPSRC's provision for Overseas Travel Grants to permit Dr Low to visit Professor Hill's laboratory at the Australian National University's Research School of Chemistry (RSC). Whilst at the RSC, PJL will gain first hand experience in the hydroruthenation chemistry used by Hill in many of his elegant investigations. It is anticipated that at the conclusion of this relatively short (3 month) visit that the new Low-Hill colloboration, based upon the exploration of this novel area of chemistry, will be well established.