Sarkar Debotra, Vasko Petra, Gluharev Tihomir, Griffin Liam P, Bogle Charlotte, Struijs Job, Tang Jianqin, Roper Aisling F, Crumpton Agamemnon E, Aldridge Simon
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Park Road, Oxford, OX1 3QR, UK.
Department of Chemistry, University of Helsinki, A. I. Virtasen Aukio 1, P.O. Box 55, Helsinki, FI-00014, Finland.
Angew Chem Int Ed Engl. 2024 Aug 5;63(32):e202407427. doi: 10.1002/anie.202407427. Epub 2024 Jul 2.
By exploiting the electronic capabilities of the N-heterocyclic boryloxy (NHBO) ligand, we have synthesized "naked" acyclic gallyl [Ga{OB(NDippCH)}] and indyl [In{OB(NDippCH)}] anions (as their [K(2.2.2-crypt)] salts) through K abstraction from [KGa{OB(NDippCH)}] and [KIn{OB(NDippCH)}] using 2.2.2-crypt. These systems represent the first O-ligated gallyl/indyl systems, are ultimately accessed from cyclopentadienyl Ga/In precursors by substitution chemistry, and display nucleophilic reactivity which is strongly influenced by the presence (or otherwise) of the K counterion.
通过利用氮杂环硼氧基（NHBO）配体的电子特性，我们使用2.2.2-穴醚从[KGa{OB(NDippCH)}]和[KIn{OB(NDippCH)}]中夺取钾，合成了“裸露的”无环烯丙基[Ga{OB(NDippCH)}]和吲哚基[In{OB(NDippCH)}]阴离子（作为它们的[K(2.2.2-穴醚)]盐）。这些体系代表了首个氧配位的烯丙基/吲哚基体系，最终通过取代化学从环戊二烯基镓/铟前体获得，并且表现出亲核反应性，这种反应性受到钾抗衡离子的存在（或不存在）的强烈影响。
