Nachtigall Olaf, Spandl Johann
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34-36, 14195, Berlin, Germany.
Chemistry. 2018 Feb 21;24(11):2785-2789. doi: 10.1002/chem.201800041. Epub 2018 Feb 6.
We report the synthesis, post-functionalization, and redox behavior of two organically functionalized aggregates, [V O (OMe) {(OCH ) C-CH N }] and [V O (OMe) {(OCH ) C-NH }]. All twelve μ -oxo groups on the edges of the Lindqvist-type {V O } core were replaced by alkoxo ligands. The absence of a negative charge and the closed organic shell make these neutral mixed-valence compounds very stable towards hydrolysis and well soluble in almost all common organic solvents. These are important advantages over classical POMs. By post-functionalization through copper(I)-catalyzed Huisgen cycloaddition or imine formation, various organic moieties could be introduced. Even a well-soluble trimer composed of three hexanuclear vanadium units connected through an aromatic triimino core was synthesized and studied. The diverse redox behavior, the versatile reactivity, the good stability, and the excellent solubility make our vanadium compounds highly interesting for applications as building blocks in macromolecular chemistry as well as redox labels in biochemistry.
我们报道了两种有机功能化聚集体[VO(OMe){(OCH₂)₂C-CH₂N₂}]和[VO(OMe){(OCH₂)₂C-NH₂}]的合成、后功能化及氧化还原行为。Lindqvist型{V₆O₁₈}核边缘的所有十二个μ-氧原子均被烷氧基配体取代。由于不带负电荷且具有封闭的有机壳层，这些中性混合价化合物对水解非常稳定，并且几乎可溶于所有常见有机溶剂。与传统的多金属氧酸盐相比，这些是重要的优势。通过铜(I)催化的Huisgen环加成反应或亚胺形成进行后功能化，可以引入各种有机基团。甚至还合成并研究了一种由通过芳香族三亚氨基核心连接的三个六核钒单元组成的可溶三聚体。多样的氧化还原行为、广泛的反应活性、良好的稳定性以及出色的溶解性，使得我们的钒化合物作为大分子化学中的结构单元以及生物化学中的氧化还原标记物具有极高的应用价值。
