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A New Generation of All-Carbon Bridged Bimetallic Complexes featuring Redox-Active, Group 6 Metal End-Caps.

新一代全碳桥双金属配合物，具有氧化还原活性、第 6 族金属端盖。

基本信息

批准号：
EP/E02582X/1
负责人：
Paul Low
金额：
$ 17.54万
依托单位：
Durham University
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2007
资助国家：
英国
起止时间：
2007 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FE02582X%2F1
关键词：
New Generation Carbon Bridged Bimetallic

项目摘要

Metal-stabilised carbon chains [M-(CC)x-M]n+ have attracted increasing interest over the last 10 years, mainly due to the remarkable changes in electronic structure which accompany changes in the formal oxidation state of the compounds. While much of this work has focussed on homobimetallic examples, recent synthetic advances make heterometallic examples accessible. This is a particularly exciting development as much of the work with homometallic polycarbon complexes has shown that distinctly different properties are imposed by different supporting metal fragments.The objective of this work is to synthesise and investigate the electronic properties of a series of compounds of the type [M-(CC)x-M']n+ in which the linking group Cx is an unsaturated carbon chain of four or more carbons and the metal end-caps M and M' are redox active, organometallic centres. A range of oxidation states (n = 0-4) is accessible of which some are stable, isolable systems. The electronic structures of this fascinating class of complexes are strongly dependent upon the identity of M and M'. However previous work has been restricted essentially to end-caps of group 7 and 8 transition metal centres of iron, ruthenium and rhenium in which the 3d metal centre Fe is much more strongly donating than the 4d/5d centres of Ru and Re. The innovation in this work is to include an organometallic end-cap featuring the group 6 metal molybdenum which is both strongly electron donating and based upon a 4d centre - this provides a unique opportunity to delineate the effect of end-cap electron donor capacity vs. metal transition series upon electronic structure. Further advantages that can be enjoyed through the introduction of Mo based end-cap group are the availability of a highly resolved spectroscopic handle (EPR) with which to investigate electronic structure by a direct experimental probe and the potential to control electronic structure in oxidised forms of the mixed group 6/group 8 heterobimetallics [M-(CC)x-M']n+ by control of molecular configuration.The work is of importance because it will lead to an enhanced understanding of the electronic structure of the unsaturated all-carbon bridge, and how this can be controlled as a function of the metal, the supporting ligands and the length of the carbon fragment. Although many talk of the need for such detailed understanding in the design of molecular components for future molecular based electronics, our goal is to arrive at a full understanding of the underlying chemistry in these metal-stabilised carbon fragments, free of the restrictions imposed by the reliance on one signature metal end-cap.

金属稳定碳链[M-(CC)x-M]n+在过去10年中引起了越来越多的兴趣，主要是由于电子结构的显著变化伴随着化合物形式氧化态的变化。虽然大部分工作都集中在同双金属的例子上，但最近的合成进展使异金属的例子变得容易获得。这是一个特别令人兴奋的发展，因为许多同金属聚碳配合物的工作已经表明，不同的支撑金属碎片施加了明显不同的性能。本工作的目的是合成并研究一系列[M-(CC)x-M′]n+型化合物的电子性质，其中连接基团Cx是四个或更多碳的不饱和碳链，金属端帽M和M′是氧化还原活性的有机金属中心。氧化态的范围（n = 0-4）是可接近的，其中一些是稳定的，可分离的系统。这类令人着迷的配合物的电子结构强烈依赖于M和M'的同一性。然而，以前的工作主要局限于铁的第7族和第8族过渡金属中心的端帽，在钌和铼中，3d金属中心Fe比Ru和Re的4d/5d中心具有更强的供电子性。这项工作的创新之处在于包括一个有机金属端盖，其特征是6族金属钼，它既具有强的供电子性，又基于4d中心-这提供了一个独特的机会来描述端盖电子供体能力与金属跃迁系列对电子结构的影响。通过引入Mo基端帽基团，可以享受到的进一步优势是高分辨率光谱手柄（EPR）的可用性，通过直接实验探针来研究电子结构，以及通过控制分子构型来控制混合6族/ 8族杂金属[M-(CC)x-M']n+的氧化形式的电子结构。这项工作很重要，因为它将有助于加深对不饱和全碳桥的电子结构的理解，以及如何将其控制为金属、支撑配体和碳片段长度的函数。尽管许多人都在谈论在未来分子电子元件的分子组件设计中需要如此详细的了解，但我们的目标是全面了解这些金属稳定碳碎片的潜在化学成分，而不受依赖于一个标志性金属端盖的限制。