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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).
ISSN: 1433-7851
Rights: © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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