Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms
Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms
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DOI：
10.1021/jacs.1c09901
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发表时间：
2021-12-23
影响因子：
15
通讯作者：
Nuckolls, Colin
中科院分区：
文献类型：
--
作者：
Reed, Douglas A.;Hochuli, Taylor J.;Nuckolls, Colin
我们表明，从一个单一的超原子基序的反应途径可以通过外部配体球的微妙的电子修饰控制。Chevrel型[Co6Se8L6]（L = PR 3，CO）超原子被用来形成卡宾封端的团簇，其反应活性可以通过周围配体的电子效应来影响。这种卡宾为配体取代化学提供了新的途径，用于选择性地安装氰化物或吡啶配体，这些配体以前在这些钴基簇中无法获得。周围的配体也影响这种卡宾的能力，以创建更大的融合簇的类型[Co12Se16L10]，提供集群融合机制的基础信息。我们使用这些信息来开发与功能化的表面配体与位点特异性，把新的配体在这个各向异性的核心上的特定位置创建二聚簇的方法。最后，调整的卡宾中间体也可以用来扰乱的[Co6Se8]核心本身的几何形状，因为我们证明了与multicarbene加合物，显示一个基本上各向异性的核心。这些额外的合成控制水平可以证明有助于将超原子簇用于许多应用，包括催化，电子器件和创建新的扩展结构。
We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [Co6Se8L6] (L = PR3, CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters. The surrounding ligands also impact the ability of this carbene to create larger fused clusters of the type [Co12Se16L10], providing underlying information for cluster fusion mechanisms. We use this information to develop methods of creating dimeric clusters with functionalized surface ligands with site specificity, putting new ligands in specific positions on this anisotropic core. Finally, adjusting the carbene intermediates can also be used to perturb the geometry of the [Co6Se8] core itself, as we demonstrate with a multicarbene adduct that displays a substantially anisotropic core. These additional levels of synthetic control could prove instrumental for using superatomic clusters for many applications including catalysis, electronic devices, and creating novel extended structures.