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https://hdl.handle.net/10356/105121
Title: | Group II metal complexes of the germylidendiide dianion radical and germylidenide anion | Authors: | Chia, Siew-Peng Carter, Emma Xi, Hong-Wei Li, Yongxin So, Cheuk-Wai |
Keywords: | DRNTU::Science::Chemistry | Issue Date: | 2014 | Source: | Chia, S.-P., Carter, E., Xi, H.-W., Li, Y., & So, C.-W. (2014). Group II metal complexes of the germylidendiide dianion radical and germylidenide anion. Angewandte chemie international edition, 53(32), 8455-8458. | Series/Report no.: | Angewandte chemie international edition | Abstract: | The two-electron reduction of a Group 14-element(I) complex [RË⋅] (E=Ge, R=supporting ligand) to form a novel low-valent dianion radical with the composition [RË:]. 2− is reported. The reaction of [LGeCl] (1, L=2,6-(CH[DOUBLE BOND]NAr)2C6H3, Ar=2,6-iPr2C6H3) with excess calcium in THF at room temperature afforded the germylidenediide dianion radical complex [LGe]. 2−⋅Ca(THF)32+ (2). The reaction proceeds through the formation of the germanium(I) radical [LGe⋅], which then undergoes a two-electron reduction with calcium to form 2. EPR spectroscopy, X-ray crystallography, and theoretical studies show that the germanium center in 2 has two lone pairs of electrons and the radical is delocalized over the germanium-containing heterocycle. In contrast, the magnesium derivative of the germylidendiide dianion radical is unstable and undergoes dimerization with concurrent dearomatization to form the germylidenide anion complex [C6H3-2-{C(H)[DOUBLE BOND]NAr}Ge-Mg-6-{C(H)-NAr}]2 (3). | URI: | https://hdl.handle.net/10356/105121 http://hdl.handle.net/10220/20658 |
ISSN: | 1433-7851 | DOI: | 10.1002/anie.201404357 | Schools: | School of Physical and Mathematical Sciences School of Chemical and Biomedical Engineering |
Rights: | © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | Fulltext Permission: | none | Fulltext Availability: | No Fulltext |
Appears in Collections: | SPMS Journal Articles |
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