High‐Yielding Synthesis of a Hetero‐Pacman Compound and the Characterization of Intermediates and Side‐Products
High‐Yielding Synthesis of a Hetero‐Pacman Compound and the Characterization of Intermediates and Side‐Products
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DOI：
10.1002/ejic.201402459
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发表时间：
2014-09
影响因子：
2.3
通讯作者：
M. Schwalbe;P. Wrzolek;G. Lal;B. Braun
中科院分区：
文献类型：
--
作者：
M. Schwalbe;P. Wrzolek;G. Lal;B. Braun
通过优化的合成程序，金属配体 5 具有包含卟啉和三联吡啶部分的异质 Pacman 支架，通过双铃木反应组装而成。在后续步骤中，在金属配体 5 的三联吡啶配位位点引入钌-联吡啶片段，形成配合物 6，该配合物得到了充分表征，并测试了其在水氧化催化中的潜在应用。在两步合成过程中分离并表征了许多副产物，包括通过碱辅助重排衍生的硼酸取代前体分子的羟基化形式。本文描述的化合物将 Pacman 概念扩展到具有不同配位球的不同金属组合的组装以及它们在小分子活化中的相互作用。
Through an optimized synthetic procedure, metalloligand 5, which features a hetero-Pacman scaffold comprising a porphyrin and a terpyridine moiety, has been assembled by a double Suzuki reaction. In a subsequent step, a ruthenium-bipyridine fragment was introduced at the terpyridine coordination site of metalloligand 5 to form complex 6, which was fully characterized and its potential application in water oxidation catalysis tested. A number of side-products were isolated and characterized during the two-step synthesis procedure, including a hydroxylated version of the boronic acid substituted precursor molecule derived by a base-assisted rearrangement. The compounds described herein extend the Pacman concept to the assembly of different metal combinations with different coordination spheres and their interactions in the activation of small molecules.