Donor substituted alkynes as directional bridging ligands in polynuclear complexes

供体取代的炔烃作为多核配合物中的定向桥连配体

• 批准号: 272575417
• 负责人: Professor Dr. Wolfram W. Seidel
• 金额: --
• 依托单位: Metallorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/272575417?language=en
• 关键词: Donor; substituted; alkynes; directional; bridging

The background of the intended research project is highlighted by the remarkable properties of supramolecular coordination compounds, in which specific alkyne ligands ensure strong intermetallic coupling. The linkage of different metal centers is accomplished by alkyne ligands, which bear donor groups in both alpha-positions. Side-on coordination at the triple bond turns the primarily linear alkynes into kappa2-chelate ligands. The donor centers can be a chalcogen- or a pnicogen atom. Mononuclear complexes with terminal donor groups may be regarded as functional ligands. The large bite angles due to the bend back angle in the alkyne complex moiety, the high polarizability and the prevalent redox activity of alkyne complexes with mid transition metals may lead to an unconventional coordination behavior. The specific function of these directional bridging ligands for the characteristics of their polynuclear complexes will be elucidated by a systematic variation of the donor centers.The main topic of the research project is the development of synthetic strategies for the controlled and stepwise preparation of polynuclear complexes featuring alkynes with alpha-donor centers. In turn, this goal depends on a straightforward access to alkyne complexes with free terminal donors from corresponding W(II)- or W(IV) acetylene or halogenacetylene complexes via nucleophilic substitution. Such substitution reactions on the coordinated alkyne were only sporadically and not systematically investigated. In addition to the assembling of polynuclear coordination compounds, the synthesis of otherwise difficult to make alkynes might be possible by this strategy. The electronic structures of the obtained polynuclear complexes will be comprehensively studied by spectroscopy and theory. On this basis a comparative classification and evaluation with respect to potential applications of these novel ligand systems will be accomplished.

超分子配位化合物的显著特性突出了预期研究项目的背景，其中特定的炔配体确保了强金属间耦合。不同金属中心的连接是通过炔配体完成的，其在两个α-位置上都带有供体基团。在三键处的侧配位将主要线性炔转变成kappa 2-螯合配体。施主中心可以是硫族元素或磷族元素原子。具有末端供体基团的单核苷酸络合物可被视为功能配体。由于炔配合物中的弯曲角、高极化率和普遍的氧化还原活性，炔配合物具有非常规的配位行为。这些定向桥连配体的多核配合物的特性的具体功能将阐明由一个系统的变化的供体centers.The研究项目的主要课题是控制和逐步制备的多核配合物具有α-供体centers. The的合成策略的发展。反过来，这一目标取决于一个直接获得的炔配合物与自由末端供体从相应的W（II）或W（IV）乙炔或卤代乙炔配合物通过亲核取代。配位炔上的这种取代反应只是零星的，没有系统的研究。除了组装多核配位化合物外，通过这种策略可能合成难以合成的炔。所得多核配合物的电子结构将通过光谱和理论进行全面研究。在此基础上，对这些新型配体体系的潜在应用进行了比较分类和评价。